Electrolytic solution and battery

ABSTRACT

A battery capable of improving the storage characteristics and the cycle characteristics is provided. The battery includes a cathode, an anode, and an electrolytic solution. The electrolytic solution is impregnated in a separator provided between the cathode and the anode. A solvent of the electrolytic solution contains a given sulfone compound such as bis(trimethylsilyl)methanedisulfonate. Compared to a case that a solvent contains other sulfone compound such as bis(methyl)methanedisulfonate, the chemical stability of the electrolytic solution is improved, and the decomposition reaction of the electrolytic solution is prevented.

CROSS REFERENCES TO RELATED APPLICATIONS

The present application claims priority to Japanese Patent ApplicationJP 2006-330835 filed in the Japanese Patent Office on Dec. 7, 2006, theentire contents of which is being incorporated herein by reference.

BACKGROUND

The present application relates to an electrolytic solution containing asolvent and an electrolyte salt and a battery using the electrolyticsolution.

In recent years, portable electronic devices such as combination cameras(videotape recorder), mobile phones, and notebook personal computershave been widely used, and it is strongly demanded to reduce their sizeand weight and to achieve their long life. Accordingly, as a powersource for the portable electronic devices, a battery, in particular alight-weight secondary batter capable of providing a high energy densityhas been developed.

Specially, a secondary battery using insertion and extraction of lithiumfor charge and discharge reaction (so-called lithium ion secondarybattery) or a secondary battery using precipitation and dissolution oflithium (so-called lithium metal secondary battery) is extremelyprospective, since such a lithium ion secondary battery or such alithium metal secondary battery can provide a higher energy densitycompared to a lead battery and a nickel cadmium battery.

In such a secondary battery, an electrolytic solution in which anelectrolyte salt such as lithium hexafluorophosphate is dissolved in anester carbonate solvent such as propylene carbonate and diethylcarbonate is widely used (for example, refer to Japanese Patent No.3294400). In particular, for improving the storage characteristics, thecycle characteristics and the like, an electrolytic solution containing,for example, derivative of a cyclic disulfonate or a chain disulfonate,a silane compound having a sulfonyl group, or a compound having asulfonyl group and a silyl group is also used (for example, refer toJapanese Unexamined Patent Application Publication Nos. 2000-133304,2002-033127, 2002-359001, and 2004-281325).

SUMMARY

In the recent electronic devices, there is a tendency that the calorificvalue is more and more increased associated with factors such as highperformance of electronic parts typified by a CPU (central processingunit). Thus, the secondary battery is exposed in the high temperatureatmosphere, and thereby the storage characteristics tend to be lowered.Furthermore, there is a tendency that the high performance and themulti-functions of the electronic devices are increasingly developed.Thus, there is a tendency that the discharge capacity is easily loweredby frequently repeating charge and discharge of the secondary battery.Therefore, it is aspired that the storage characteristics and the cyclecharacteristics of the secondary battery could be further improved.

In view of the foregoing, it is desirable to provide an electrolyticsolution and a battery capable of improving the storage characteristicsand the cycle characteristics.

According to an embodiment, there is provided an electrolytic solutionthat contains a solvent containing a sulfone compound shown in Chemicalformula 1 and an electrolyte salt.

R11 represents an a-valence group composed of carbon and an elementselected from the group consisting of hydrogen, oxygen, and halogen. Thecarbon atom thereof is bonded to a sulfur atom in a sulfonyl group. R12,R13, and R14 are an alkyl group with the carbon number in the range from1 to 4, an alkylene group with the carbon number in the range from 1 to4, or an aryl group. R12, R13, and R14 may be identical or different. arepresents one of integer numbers 2 or more.

According to an embodiment of the application, there is provided abattery including a cathode, an anode, and an electrolytic solution,wherein the electrolytic solution contains a solvent containing asulfone compound shown in Chemical formula 1 and an electrolyte salt.

R11 represents an a-valence group composed of carbon and an elementselected from the group consisting of hydrogen, oxygen, and halogen. Thecarbon atom thereof is bonded to a sulfur atom in a sulfonyl group. R12,R13, and R14 are an alkyl group with the carbon number in the range from1 to 4, an alkylene group with the carbon number in the range from 1 to4, or an aryl group. R12, R13, and R14 may be identical or different. arepresents one of integer numbers 2 or more.

According to the electrolytic solution of an embodiment, the solventcontains the sulfone compound shown in Chemical formula 1. Therefore,compared to a case that the solvent does not contain the sulfonecompound, the chemical stability is improved, and the decompositionreaction is prevented when the electrolytic solution is used for anelectrochemical device such as a battery. Thereby, in a battery usingthe electrolytic solution according to the embodiment of theapplication, the storage characteristics and the cycle characteristicscan be improved.

Additional features and advantages are described herein, and will beapparent from, the following Detailed Description and the figures.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a cross section showing a structure of a first battery usingan electrolytic solution according to an embodiment;

FIG. 2 is a cross section showing an enlarged part of a spirally woundelectrode body shown in FIG. 1;

FIG. 3 is an exploded perspective view showing a structure of a forthbattery using the electrolytic solution according to an embodiment; and

FIG. 4 is a cross section showing a structure taken along line IV-IV ofa spirally wound electrode body shown in FIG. 3.

DETAILED DESCRIPTION

An embodiment will be hereinafter described in detail with reference tothe drawings.

An electrolytic solution according to an embodiment is used for, forexample, an electrochemical device such as a battery. The electrolyticsolution according to an embodiment contains a solvent containing thesulfone compound shown in Chemical formula 1 and an electrolyte salt.Since the solvent contains the sulfone compound, the chemical stabilityis improved, and thus the decomposition reaction is prevented when theelectrolytic solution is used for the electrochemical device. Thereby,the storage characteristics and the cycle characteristics in theelectrochemical device are improved. The carbon number of R12 to R14 inChemical formula 1 are in the range from 1 to 4, since therebysufficient solubility can be obtained.

In the formula, R11 represents an a-valence group composed of carbon andan element selected from the group consisting of hydrogen, oxygen, andhalogen. The carbon atom thereof is bonded to a sulfur atom in asulfonyl group. R12, R13, and R14 are an alkyl group with the carbonnumber in the range from 1 to 4, an alkylene group with the carbonnumber in the range from 1 to 4, or an aryl group. R12, R13, and R14 maybe identical or different. a represents one of integer numbers 2 ormore.

The content of the sulfone compound shown in Chemical formula 1 in theelectrolytic solution is preferably in the range from 0.01 wt % to 5 wt%, since thereby sufficient effects can be obtained.

The molecular weight of the sulfone compound shown in Chemical formula 1is preferably in the range from 300 to 2000, more preferably in therange from 300 to 1000, and much more preferably in the range from 300to 650. Thereby, sufficient effects can be obtained, and sufficientsolubility can be obtained.

The sulfone compounds shown in Chemical formula 1 preferably include thesulfone compound shown in Chemical formula 2. Thereby, sufficienteffects can be obtained, and sufficient solubility can be obtained. Thesulfone compound shown in Chemical formula 2 is a compound in which ashown in Chemical formula 1 is 2 and R11 is a bivalent group.

In the formula, R21 represents a bivalent group composed of carbon andan element selected from the group consisting of hydrogen, oxygen, andhalogen. The carbon atom thereof is bonded to a sulfur atom in asulfonyl group. R22, R23, and R24 are an alkyl group with the carbonnumber in the range from 1 to 4, an alkylene group with the carbonnumber in the range from 1 to 4, or an aryl group. R22, R23, and R24 maybe identical or different.

R21 shown in Chemical formula 2 includes, for example, —CH₂—, —CHF—,CF₂—, —C≡C—, —CH₂—CH₂—, —CF₂—CF₂—, —CH₂—O—CH₂—, —CF₂—CH₂—CF₂—,—CH₂—CH₂—CH₂—, —CF₂—CF₂—CF₂—, —CH₂—CH₂—CH₂—CH₂—, —CF₂—CH₂—CH₂—CF₂—,—CF₂—CF₂—CF₂—CF₂—, —C(CH₃)₂—, —C(C₂H₅)₂—, —C(C₃H₇)₂—, —C(CH₃)₂—C(CH₃)₂—,—CH₂—CH₂—C(CH₃)₂—, —CF₂—CH₂—C(CH₃)₂—, —C(CH₃)₂—CH₂—C(CH₃)₂—,—C(C₆H₅)₂—C(C₆H₅)₂—, —CF₂—CH₂—C(C₆H₅)₂—, —C(C₆H₅)₂—CH₂—C(C₆H₅)₂— and thelike. It is needless to say that R21 is not limited to the foregoinggroups, and R21 may be other group as long as such a group has thestructure shown in Chemical formula 2.

—Si(R22)(R23)(R24) shown in Chemical formula 2 includes, for example,—Si(CH₃)₃, —Si(C₂H₅)₃, —Si(C₃H₇)₃, —Si(C₄H₉)₃, —Si(C₆H₅)₃,—Si(CH₃)₂(C₂H₅), —Si(CH₃)(C₂H₅)₂, —Si(C₂H₅)(C₃H₇)₂, —Si(C₂H₅)₂(C₃H₇),—Si(CH(CH₃)₂)₃, —Si(CH₃)(CH(CH₃)₂)₂, —Si(CH₃)₂(CH(CH₃)₂),—Si(C₂H₅)(CH(CH₃)₂)₂, —Si(C₂H₅)₂(CH(CH₃)₂) and the like. It is needlessto say that —Si(R22)(R23)(R24) is not limited to the foregoing groups,and —Si(R22)(R23)(R24) may be other group as long as such a group hasthe structure shown in Chemical formula 2. The foregoing examples as—Si(R22)(R23)(R24) shown in Chemical formula 2 can be similarly appliedto —Si(R12)(R13)(R14) shown in Chemical formula 1.

As a representative of the sulfone compound shown in Chemical formula 1,examples of the sulfone compound shown in Chemical formula 2 includebis(trimethylsilyl)methanedisulfonate shown in Chemical formula 3 andthe like.

In addition, the sulfone compound shown in Chemical formula 2 includes,for example, bis(triethylsilyl)methanedisulfonate,bis(tripropylsilyl)methanedisulfonate,bis(tributylsilyl)methanedisulfonate,bis(triisopropylsilyl)methanedisulfonate,bis(trimethylsilyl)-2,2-difluoromethanedisulfonate,bis(triethylsilyl)-2,2-difluorodisulfonate,bis(tripropylsilyl)-2,2-difluoromethanedisulfonate,bis(tributylsilyl)-2,2-difluoromethanedisulfonate,bis(triisopropylsilyl)-2,2-difluoromethanedisulfonate,bis(diethylmethylsilyl)-2,2-difluoromethanedisulfonate,bis(dipropylmethylsilyl)-2,2-difluoromethanedisulfonate,bis(dibutylmethylsilyl)-2,2-difluoromethanedisulfonate,bis(diisopropylmethylsilyl)-2,2-difluoromethanedisulfonate,bis(dimethylethylsilyl)-2,2-difluoromethanedisulfonate,bis(dimethylbutylsilyl)-2,2-difluoromethanedisulfonate,bis(dimethylpropylsilyl)-2,2-difluoromethanedisulfonate,bis(dibutylisopropylsilyl)-2,2-difluoromethanedisulfonate,bis(trimethylsilyl)-2,2-dimethylmethanedisulfonate,bis(triethylsilyl)-2,2-dimethylmethanedisulfonate,bis(tripropylsilyl)-2,2-dimethylmethanedisulfonate,bis(tributylsilyl)-2,2-dimethylmethanedisulfonate,bis(triisopropylsilyl)-2,2-dimethylmethanedisulfonate,bis(trimethylsilyl)-2,2-diphenylmethanedisulfonate,bis(triethylsilyl)-2,2-diphenylmethanedisulfonate,bis(tripropylsilyl)-2,2-diphenylmethanedisulfonate,bis(tributylsilyl)-2,2-diphenylmethanedisulfonate,bis(triisopropylsilyl)-2,2-diphenylmethanedisulfonate,bis(trimethylsilyl)acetylenedisulfonate,bis(triethylsilyl)acetylenedisulfonate,bis(tripropylsilyl)acetylenedisulfonate,bis(tributylsilyl)acetylenedisulfonate,bis(triisopropylsilyl)acetylenedisulfonate,bis(trimethylsilyl)ethanedisulfonate,bis(triethylsilyl)ethanedisulfonate,bis(tripropylsilyl)ethanedisulfonate,bis(tributylsilyl)ethanedisulfonate,bis(triisopropylsilyl)ethanedisulfonate,bis(trimethylsilyl)-2,2,3,3-tetrafluoroethanedisulfonate,bis(triethylsilyl)-2,2,3,3-tetrafluoroethanedisulfonate,bis(tripropylsilyl)-2,2,3,3-tetrafluoroethanedisulfonate,bis(tributylsilyl)-2,2,3,3-tetrafluoroethanedisulfonate,bis(triisopropylsilyl)-2,2,3,3-tetrafluoroethanedisulfonate,bis(trimethylsilyl)propanedisulfonate,bis(triethylsilyl)propanedisulfonate,bis(tripropylsilyl)propanedisulfonate,bis(tributylsilyl)propanedisulfonate,bis(triisopropylsilyl)propanedisulfonate,bis(trimethylsilyl)-2,2,3,3,4,4-hexafluoropropanedisulfonate,bis(triethylsilyl)-2,2,3,3,4,4-hexafluoropropanedisulfonate,bis(tripropylsilyl)-2,2,3,3,4,4-hexafluoropropanedisulfonate,bis(tributylsilyl)-2,2,3,3,4,4-hexafluoropropanedisulfonate,bis(triisopropylsilyl)-2,2,3,3,4,4-hexafluoropropanedisulfonate and thelike.

One of the foregoing may be used singly, or two or more thereof may beused by mixing. Specially, as the sulfone compound shown in Chemicalformula 2, bis(trimethylsilyl)methanedisulfonate is preferable, sincethereby sufficient effects can be obtained, and sufficient solubilitycan be obtained. It is needless to say that the sulfone compound is notlimited to the foregoing compounds, and the sulfone compound may beother compound as long as such a compound has the structure shown inChemical formula 1.

The solvent preferably contains, for example, cyclic ester carbonatehaving an unsaturated bond. Thereby, in the electrochemical deviceincluding the electrolytic solution, the decomposition reaction of theelectrolytic solution can be more prevented. Accordingly, the storagecharacteristics and the cycle characteristics are more improved. As thecyclic ester carbonate having an unsaturated bond, for example, at leastone selected from the group consisting of vinylene carbonate compounds,vinyl ethylene carbonate compounds, and methylene ethylene carbonatecompounds can be cited.

The vinylene carbonate compounds include, for example, vinylenecarbonate (1,3-dioxole-2-one), methyl vinylene carbonate(4-methyl-1,3-dioxole-2-one), ethyl vinylene carbonate(4-ethyl-1,3-dioxole-2-one), 4,5-dimethyl-1,3-dioxole-2-one,4,5-diethyl-1,3-dioxole-2-one, 4-fluoro-1,3-dioxole-2-one,4-trifluoromethyl-1,3-dioxole-2-one and the like.

The vinyl ethylene carbonate compounds include, for example, vinylethylene carbonate (4-vinyl-1,3-dioxolane-2-one),4-methyl-4-vinyl-1,3-dioxolane-2-one,4-ethyl-4-vinyl-1,3-dioxolane-2-one,4-n-propyl-4-vinyl-1,3-dioxolane-2-one,5-methyl-4-vinyl-1,3-dioxolane-2-one, 4,4-divinyl-1,3-dioxolane-2-one,4,5-divinyl-1,3-dioxolane-2-one and the like.

The methylene ethylene carbonate compounds include4-methylene-1,3-dioxolane-2-one,4,4-dimethyl-5-methylene-1,3-dioxolane-2-one,4,4-diethyl-5-methylene-1,3-dioxolane-2-one and the like.

One of the foregoing may be used singly, or two or more thereof may beused by mixing. Specially, as the cyclic ester carbonate having anunsaturated bond, at least one selected from the group consisting ofvinylene carbonate and vinyl ethylene carbonate is preferable, sincethereby sufficient effects can be obtained. In this case, in particular,vinylene carbonate is more preferable than vinyl ethylene carbonate,since thereby higher effects can be obtained.

The solvent preferably contains at least one selected from the groupconsisting of chain ester carbonate having a halogen as an element shownin Chemical formula 4 and cyclic ester carbonate having a halogen as anelement shown in Chemical formula 5. Thereby, in the electrochemicaldevice including the electrolytic solution, a stable coat is formed onthe electrode surface, and thus the decomposition reaction of theelectrolytic solution is more prevented. Accordingly, the storagecharacteristics and the cycle characteristics are more improved.

In the formula, R31 to R36 represent a hydrogen group, a halogen group,an alkyl group, or an alkyl halide group. R31 to R36 may be identical ordifferent. However, at least one of R31 to R36 is the halogen group orthe alkyl halide group.

In the formula, R41 to R44 represent a hydrogen group, a halogen group,an alkyl group, or an alkyl halide group. R41 to R44 may be identical ordifferent. However, at least one of R41 to R44 is the halogen group orthe alkyl halide group.

The chain ester carbonate having a halogen as an element shown inChemical formula 4 includes, for example, fluoromethyl methyl carbonate,bis(fluoromethyl) carbonate, difluoromethyl methyl carbonate and thelike. One thereof may be used singly, or two or more thereof may be usedby mixing.

The cyclic ester carbonate having a halogen as an element shown inChemical formula 5 includes, for example, a compounds shown in Chemicalformulas 6 and 7, that is, 4-fluoro-1,3-dioxolane-2-one in Chemicalformula 6(1), 4-chloro-1,3-dioxolane-2-one in Chemical formula 6(2),4,5-difluoro-1,3-dioxolane-2-one in Chemical formula 6(3),tetrafluoro-1,3-dioxolane-2-one in Chemical formula 6(4),4-fluoro-5-chloro-1,3-dioxolane-2-one in Chemical formula 6(5),4,5-dichloro-1,3-dioxolane-2-one in Chemical formula 6(6),tetrachloro-1,3-dioxolane 2-one in Chemical formula 6(7),4,5-bistrifluoromethyl-1,3-dioxolane 2-one in Chemical formula 6(8),4-trifluoromethyl-1,3-dioxolane-2-one in Chemical formula 6(9),4,5-difluoro-4,5-dimethyl-1,3-dioxolane-2-one in Chemical formula 6(10),4-methyl-5,5-difluoro-1,3-dioxolane-2-one in Chemical formula 6(11),4-ethyl-5,5-difluoro-1,3-dioxolane-2-one in Chemical formula 6(12) andthe like; and 4-trifluoromethyl-5-fluoro-1,3-dioxolane-2-one in Chemicalformula 7(1), 4-trifluoromethyl-5-methyl-1,3-dioxolane-2-one in Chemicalformula 7(2), 4-fluoro-4,5-dimethyl-1,3-dioxolane-2-one in Chemicalformula 7(3), 4,4-difluoro-5-(1,1-difluoroethyl)-1,3-dioxolane-2-one inChemical formula 7(4), 4,5-dichloro-4,5-dimethyl-1,3-dioxolane-2-one inChemical formula 7(5), 4-ethyl-5-fluoro-1,3-dioxolane-2-one in Chemicalformula 7(6), 4-ethyl-4,5-difluoro-1,3-dioxolane-2-one in Chemicalformula 7(7), 4-ethyl-4,5,5-trifluoro-1,3-dioxolane-2-one in Chemicalformula 7(8), 4-fluoro-4-methyl-1,3-dioxolane-2-one in Chemical formula7(9) and the like. One thereof may be used singly, or two or morethereof may be used by mixing. Specially, as the cyclic ester carbonatehaving a halogen as an element, at least one selected from the groupconsisting of 4-fluoro-1,3-dioxolane-2-one and4,5-difluoro-1,3-dioxolane-2-one is preferable, since these cyclic estercarbonates are easily available, and can provide sufficient effects. Inthis case, in particular, 4,5-difluoro-1,3-dioxolane-2-one is morepreferable than 4-fluoro-1,3-dioxolane-2-one, since thereby highereffects can be obtained. More specifically, as4,5-difluoro-1,3-dioxolane-2-one, a trans isomer is more preferable thana cis isomer to obtain higher effects.

Further, the solvent preferably contains sultone (cyclic sulfonate) oran acid anhydride. Thereby, in the electrochemical device including theelectrolytic solution, the decomposition reaction of the electrolyticsolution is further suppressed. Accordingly, the storage characteristicsand the cycle characteristics are further improved.

Sultone includes, for example, propane sultone, propene sultone and thelike. One thereof may be used singly, or two or more thereof may be usedby mixing. Specially, as the sultone, propene sultone is preferable. Thecontent of the sultone in the electrolytic solution is preferably in therange from 0.5 wt % to 3 wt %. Thereby, sufficient effects can beobtained.

The acid anhydride includes, for example, succinic anhydride, glutaricanhydride, maleic anhydride, sulfobenzoic anhydride, sulfopropionicanhydride, sulfobutyric anhydride and the like. One thereof may be usedsingly, or two or more thereof may be used by mixing. Specially, as theacid anhydride, at least one selected from the group consisting ofsuccinic anhydride and sulfobenzoic anhydride is preferable, sincethereby sufficient effects can be obtained. In this case, in particular,sulfobenzoic anhydride is more preferable than succinic anhydride, sincethereby higher effects can be obtained. The content of the acidanhydride in the electrolytic solution is preferably in the range from0.5 wt % to 3 wt %, since thereby sufficient effects can be obtained.

The solvent may contain, for example, other solvent (for example,nonaqueous solvent such as an organic solvent) together with theforegoing sulfone compound shown in Chemical formula 1 or the like.Other solvents include, for example, ethylene carbonate, propylenecarbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate,ethyl methyl carbonate, methylpropyl carbonate, γ-butyrolactone,γ-valerolactone, 1,2-dimethoxyethane, tetrahydrofuran,2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane,4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, methyl acetate, ethylacetate, methyl propionate, ethyl propionate, methyl butyrate, methylisobutyrate, trimethyl methyl acetate, trimethyl ethyl acetate,acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile,3-methyoxypropionitrile, N,N-dimethylformamide, N-methylpyrrolidinone,N-methyloxazolidinone, N,N′-dimethylimidazolidinone, nitromethane,nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide,dimethyl sulfoxide phosphate and the like. One thereof may be usedsingly, or two or more thereof may be used by mixing. Specially, asother solvent, at least one selected from the group consisting ofethylene carbonate, propylene carbonate, dimethyl carbonate, diethylcarbonate, and ethyl methyl carbonate is preferable. Thereby, in theelectrochemical device including the electrolytic solution, superiorcapacity characteristics, superior storage characteristics, and superiorcycle characteristics can be obtained. In this case, in particular, thesolvent preferably contains a mixture of a high-viscosity (highdielectric constant) solvent (for example, dielectric constant ∈≧30)such as ethylene carbonate and propylene carbonate and a low-viscositysolvent (for example, viscosity ≦1 mPa·s) such as dimethyl carbonate,ethyl methyl carbonate, and diethyl carbonate. Thereby, the dissociationproperty of the electrolyte salt and the ion mobility are improved, andthus higher effects can be obtained.

The electrolyte salt preferably contains at least one selected from thegroup consisting of the compounds shown in Chemical formula 8, Chemicalformula 9, and Chemical formula 10. Thereby, in the electrochemicaldevice including the electrolytic solution, sufficient conductivity canbe obtained stably, and thus the storage characteristics and the cyclecharacteristics are improved. One of the compound shown in Chemicalformulas 8 to 10 may be used singly, or two or more thereof may be usedby mixing.

In the formula, X51 represents a Group 1A element or a Group 2A elementin the short period periodic table or aluminum. M51 represents atransition metal, a Group 3B element, a Group 4B element, or a Group 5Belement in the short period periodic table. R51 represents a halogengroup. Y51 represents —OC—R52-CO—, —OC—CR53₂—, or —OC—CO—. R52represents an alkylene group, an alkylene halide group, an arylenegroup, or an arylene halide group. R53 represents an alkyl group, analkyl halide group, an aryl group, or an aryl halide group, and may beidentical or different. a5 represents one of integer numbers 1 to 4. b5represents 0 or an integer number of 2 or 4. c5, d5, m5, and n5represent one of integer numbers 1 to 3.

In the formula, X61 represents a Group 1A element or a Group 2A elementin the short period periodic table. M61 represents a transition metal, aGroup 3B element, a Group 4B element, or a Group 5B element in the shortperiod periodic table. Y61 represents —OC—(CR61₂)_(b6)—CO—,—R63₂C—(CR62₂)_(d6)—CO—, —R63₂C—(CR62₂)_(c6)—CR63₂—,—R63₂C—(CR62₂)_(c6)—SO₂—, —O₂S—(CR62₂)_(d6)—SO₂—, or—OC—(CR62₂)_(d6)—SO₂—. R61 and R63 represent a hydrogen group, an alkylgroup, a halogen group, or an alkyl halide group. R61 and R63 may berespectively identical or different. At least one of R61 and R63 isrespectively the halogen group or the alkyl halide group. R62 representsa hydrogen group, an alkyl group, a halogen group, or an alkyl halidegroup, and may be identical or different. a6, e6, and n6 represent aninteger number of 1 or 2. b6 and d6 represent one of integer numbers 1to 4. c6 represents 0 or one of integer numbers 1 to 4. f6 and m6represent one of integer numbers 1 to 3.

In the formula, X71 represents a Group 1A element or a Group 2A elementin the short period periodic table. M71 represents a transition metal, aGroup 3B element, a Group 4B element, or a Group 5B element in the shortperiod periodic table. Rf represents a fluorinated alkyl group with thecarbon number in the range from 1 to 10 or a fluorinated aryl group withthe carbon number in the range from 1 to 10. Y71 represents—OC—(CR71₂)_(d7)—CO—, —R72₂C—(CR71₂)_(d7)—CO—,—R72₂C—(CR71₂)_(d7)—CR72₂—, —R72₂C—(CR71₂)_(d7)—SO₂—,—O₂S—(CR71₂)_(e7)—SO₂—, or —OC—(CR71₂)_(e7)—SO₂—. R71 represents ahydrogen group, an alkyl group, a halogen group, or an alkyl halidegroup, and may be identical or different. R72 represents a hydrogengroup, an alkyl group, a halogen group, or an alkyl halide group, may beidentical or different, but at least one thereof is the halogen group orthe alkyl halide group. a7, f7, and n7 represent an integer number of 1or 2. b7 c7, and e7 represent one of integer numbers 1 to 4. d7represents 0 or one of integer numbers 1 to 4. g7 and m7 represent oneof integer numbers 1 to 3.

As an example of the compounds shown in Chemical formulas 8 to 10, thecompounds shown in Chemical formulas 11 and 12 can be cited.

The compound shown in Chemical formula 8 includes, for example,difluoro[oxalate-O,O′]lithium borate in Chemical formula 11(1),difluorobis[oxalate-O,O′]lithium phosphate in Chemical formula 11(2),difluoro[3,3,3-trifluoro-2-oxide-2-trifluoromethylpropionate(2-)-O,O′]lithium borate in Chemical formula 11(3),bis[3,3,3-trifluoro-2-oxide-2-trifluoromethylpropionate(2-)-O,O′]lithium borate in Chemical formula 11(4),tetrafluoro[oxalate-O,O′]lithium phosphate in Chemical formula 11(5),bis[oxalate-O,O′]lithium borate in Chemical formula 11(6) and the like.

The compound shown in Chemical formula 9 includes, for example,(2,2-difluoromalonate oxalate)lithium borate in Chemical formula 12(1),[bis(3,3,3-trifluoromethyl)glycolate oxalate]lithium borate in Chemicalformula 12(2), (3,3,3-trifluoromethyl propionate oxalate)lithium boratein Chemical formula 12(3), (2-trifluoromethyl propionate oxalate)lithiumborate in Chemical formula 12(4), (4,4,4-trifluoro-3-trifluoromethylbutyric acid oxalate)lithium borate in Chemical formula 12(5),(perfluoropinacolate oxalate)lithium borate in Chemical formula 12(6),(4,4,4-trifluoro-3-methyl butyric acid oxalate)lithium borate inChemical formula 12(7), (4,4,4-trifluoro butyric acid oxalate)lithiumborate in Chemical formula 12(8) and the like.

The compound shown in Chemical formula 10 includes, for example,fluorotrifluoromethyl[oxalate-O,O′]lithium borate in Chemical formula12(9) and the like.

One of the foregoing compounds may be used singly, or two or morethereof may be used by mixing. Specially, as the compounds shown inChemical formulas 8 to 10, at least one selected from the groupconsisting of bis[oxalate-O,O′]lithium borate and[bis(3,3,3-trifluoromethyl)glycolate oxalate]lithium borate ispreferable, since thereby sufficient effects can be obtained. It isneedless to say that the compound is not limited to the compounds shownin Chemical formulas 11 and 12, and the compound may be other compoundas long as such a compound has the structure shown in Chemical formulas8 to 10.

The electrolyte salt preferably contains, for example, other electrolytesalt together with the foregoing compound shown in Chemical formulas 8to 10. Thereby, higher effects can be obtained. Other electrolyte saltsinclude, for example, lithium hexafluorophosphate (LiPF₆), lithiumtetrafluoroborate (LiBF₄), lithium perchlorate (LiClO₄), lithiumhexafluoroarsenate (LiAsF₆), lithium tetraphenylborate (LiB(C₆H₅)₄),lithium methanesulfonate (LiCH₃SO₃), lithium trifluoromethanesulfonate(LiCF₃SO₃), lithium tetrachloroaluminate (LiAlCl₄), lithiumhexafluosilicate (Li₂SiF₆), lithium chloride (LiCl), lithium bromide(LiBr) and the like. Such other electrolyte salt may be used singly, ortwo or more thereof may be used by mixing. Specially, as otherelectrolyte salt, at least one selected from the group consisting oflithium hexafluorophosphate, lithium tetrafluoroborate, lithiumperchlorate, and lithium hexafluoroarsenate is preferable, since therebysufficient effects can be obtained. In this case, lithiumhexafluorophosphate is more preferable, since thereby the internalresistance is lowered, and thus higher effects can be obtained. Inparticular, when the electrolyte salt contains at least one selectedfrom the group consisting of the foregoing compounds shown in Chemicalformulas 8 to 10 together with lithium hexafluorophosphate,significantly high effects can be obtained.

The electrolyte salt preferably contains the compound shown in Chemicalformula 13, Chemical formula 14, and Chemical formula 15. Thereby,sufficient effects can be obtained. One thereof may be used singly, ortwo or more thereof may be used by mixing. In particular, when theelectrolyte salt contains at least one selected from the groupconsisting of the compounds shown in Chemical formulas 13 to 15 togetherwith the foregoing lithium hexafluorophosphate, significantly higheffects can be obtained.

LiN(C_(m)F_(2m+1)SO₂)(C_(n)F_(2n+1)SO₂)  Chemical formula 13

In the formula, m and n represent an integer number of 1 or more. m andn may be identical or different.

In the formula, R81 represents a straight chain or branched perfluoroalkylene group with the carbon number in the range from 2 to 4.

LiC(C_(p)F_(2p+1)SO₂)(C_(q)F_(2q+1)SO₂)(C_(r)F_(2r+1)SO₂)  Chemicalformula 15

In the formula, p, q, and r represent an integer number of 1 or more. p,q, and r may be identical or different.

The chain compound shown in Chemical formula 13 includes, for example,lithium bis(trifluoromethanesulfonyl)imide (LiN(CF₃SO₂)₂), lithiumbis(pentafluoroethanesulfonyl)imide (LiN(C₂F₅SO₂)₂), lithium(trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide(LiN(CF₃SO₂)(C₂F₅SO₂)), lithium(trifluoromethanesulfonyl)(heptafluoropropanesulfonyl)imide(LiN(CF₃SO₂)(C₃F₇SO₂)), lithium(trifluoromethanesulfonyl)(nonafluorobutanesulfonyl)imide(LiN(CF₃SO₂)(C₄F₉SO₂)) and the like. One thereof may be used singly, ortwo or more thereof may be used by mixing.

The cyclic compound shown in Chemical formula 14 includes, for example,a compounds shown in Chemical formula 16, that is, lithium1,2-perfluoroethanedisulfonylimide in Chemical formula 16(1), lithium1,3-perfluoropropanedisulfonylimide in Chemical formula 16(2), lithium1,3-perfluorobutanedisulfonylimide in Chemical formula 16(3), lithium1,4-perfluorobutanedisulfonylimide in Chemical formula 16(4) and thelike. One thereof may be used singly, or two or more thereof may be usedby mixing. Specially, as the cyclic compound shown in Chemical formula13, lithium 1,3-perfluoropropanedisulfonylimide is preferably contained,since thereby sufficient effects can be obtained.

The chain compound shown in Chemical formula 15 includes, for example,lithium tris(trifluoromethanesulfonyl)methyde (LiC(CF₃SO₂)₃) and thelike.

The content of the electrolyte salt is preferably in the range from 0.3mol/kg to 3.0 mol/kg to the solvent. If the content is out of theforegoing range, there is a possibility that the ion conductivity issignificantly lowered and thus sufficient capacity characteristics andthe like are not able to be obtained in the electrochemical deviceincluding the electrolytic solution.

According to the electrolytic solution, the solvent contains the sulfonecompound shown in Chemical formula 1. Therefore, compared to a case notcontaining the sulfone compound shown in Chemical formula 1, thechemical stability is improved, and the decomposition reaction isprevented when the electrolytic solution is used for an electrochemicaldevice such as a battery. The case not containing the sulfone compoundshown in Chemical formula 1 is the case, for example, in which thesolvent contains a sulfone compound such as(bis(methyl)methanedisulfonate) shown in Chemical formula 17 and thelike. Thus, according to the electrolytic solution, the storagecharacteristics and the cycle characteristics are improved in theelectrochemical device including the electrolytic solution. In thiscase, when the content of the sulfone compound shown in Chemical 1 inthe electrolytic solution is in the range from 0.01 wt % to 5 wt %,sufficient effects can be obtained.

In particular, when the solvent contains the cyclic ester carbonatehaving an unsaturated bond, or when the solvent contains at least oneselected from the group consisting of the chain ester carbonate having ahalogen as an element shown in Chemical formula 4 and the cyclic estercarbonate having a halogen as an element shown in Chemical formula 5,hither effects can be obtained.

Further, when the electrolyte salt contains at least one selected fromthe group consisting of the compounds shown in Chemical formulas 8 to 10and contains at least one selected from the group consisting of lithiumhexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, andlithium hexafluoroarsenate, or when the electrolyte salt contains atleast one selected from the group consisting of the compounds shown inChemical formulas 13 to 15, still higher effects can be obtained.

Next, a description will be given of a usage example of the foregoingelectrolytic solution. Taking a battery as an example of electrochemicaldevices, the electrolytic solution is used for the battery as follows.

First Battery

FIG. 1 shows a cross sectional structure of a first battery. The batteryis a so-called lithium ion secondary battery in which the anode capacityis expressed by the capacity component based on insertion and extractionof lithium as an electrode reactant. FIG. 1 shows a battery structure ofa so-called cylinder type secondary battery.

The secondary battery contains a spirally wound electrode body 20 inwhich a cathode 21 and an anode 22 are spirally wound with a separator23 in between, and a pair of insulating plates 12 and 13 inside abattery can 11 in the shape of an approximately hollow cylinder. Thebattery can 11 is made of, for example, iron (Fe) plated by nickel (Ni).One end of the battery can 11 is closed, and the other end thereof isopened. The pair of insulating plates 12 and 13 is arranged to sandwichthe spirally wound electrode body 20 in between and to extendperpendicularly to the spirally wound periphery face.

At the open end of the battery can 11, a battery cover 14, and a safetyvalve mechanism 15 and a PTC (Positive Temperature Coefficient) device16 provided inside the battery cover 14 are attached by being caulkedwith a gasket 17. Inside of the battery can 11 is thereby hermeticallysealed. The battery cover 14 is made of, for example, a material similarto that of the battery can 11. The safety valve mechanism 15 iselectrically connected to the battery cover 14 through the PTC device16. In the safety valve mechanism 15, when the internal pressure of thebattery becomes a certain level or more by internal short circuit,external heating or the like, a disk plate 15A flips to cut the electricconnection between the battery cover 14 and the spirally wound electrodebody 20. When temperature rises, the PTC device 16 increases theresistance and thereby limits a current to prevent abnormal heatgeneration resulting from a large current. The gasket 17 is made of, forexample, an insulating material and its surface is coated with asphalt.

For example, a center pin 24 is inserted in the center of the spirallywound electrode body 20. In the spirally wound electrode body 20, acathode lead 25 made of aluminum or the like is connected to the cathode21, and an anode lead 26 made of nickel or the like is connected to theanode 22. The cathode lead 25 is electrically connected to the batterycover 14 by being welded to the safety valve mechanism 15. The anodelead 26 is welded and thereby electrically connected to the battery can11.

FIG. 2 shows an enlarged part of the spirally wound electrode body 20shown in FIG. 1. The cathode 21 has a structure in which, for example, acathode active material layer 21B is provided on the both faces of acathode current collector 21A having a pair of opposed faces. Thecathode current collector 21A is made of, for example, a metal materialsuch as aluminum, nickel, and stainless. The cathode active materiallayer 21B contains, for example, as a cathode active material, one ormore cathode materials capable of inserting and extracting lithium as anelectrode reactant. If necessary, the cathode active material layer 21Bmay contain an electrical conductor, a binder and the like.

As the cathode material capable of inserting and extracting lithium, forexample, a lithium complex oxide such as lithium cobalt oxide, lithiumnickel oxide, a solid solution containing them(Li(Ni_(x)Co_(y)Mn_(z))O₂, values of x, y, and z are respectivelyexpressed as 0≦x≦1, 0≦y≦1, 0≦z≦1, and x+y+z=1), lithium manganese oxidehaving a spinel structure (LiMn₂O₄), and a solid solution thereof(Li(Mn_(2-v)Ni_(v))O₄, a value of v is expressed as v<2); or a phosphatecompound having an olivine structure such as lithium iron phosphate(LIFePO₄) is preferable. Thereby, a high energy density can be obtained.In addition to the foregoing, as the foregoing cathode material, forexample, an oxide such as titanium oxide, vanadium oxide, and manganesedioxide; a disulfide such as iron disulfide, titanium disulfide, andmolybdenum sulfide; sulfur; a conductive polymer compound such aspolyaniline and polythiophene can be cited.

The anode 22 has a structure in which, for example, an anode activematerial layer 22B is provided on the both faces of an anode currentcollector 22A having a pair of opposed faces. The anode currentcollector 22A is preferably made of a material having the favorableelectrochemical stability, the favorable electrical conductivity, andthe favorable mechanical strength. The anode current collector 22A ispreferably made of, for example, a metal material such as copper (Cu),nickel, and stainless. Specially, the anode current collector 22A ispreferably made of copper, since thereby high conductivity can beobtained. The anode active material layer 22B contains, for example, asan anode active material, one or more anode materials capable ofinserting and extracting lithium. If necessary, the anode activematerial layer 22B may contain an electrical conductor, a binder and thelike.

As the anode material capable of inserting and extracting lithium, forexample, a carbon material can be cited. As the carbon material, forexample, graphitizable carbon, non-graphitizable carbon in which thespacing of (002) plane is 0.37 nm or more, or graphite in which thespacing of (002) plane is 0.34 nm or less can be cited. Morespecifically, pyrolytic carbons, coke, graphite, glassy carbons, anorganic polymer compound fired body, carbon fiber, activated carbon,carbon black or the like can be cited. Of the foregoing, the cokeincludes pitch coke, needle coke, petroleum coke and the like. Theorganic polymer compound fired body is obtained by firing andcarbonizing a phenol resin, a furan resin or the like at an appropriatetemperature. In the carbon material, a change in the crystal structuredue to insertion and extraction of lithium is very little. Therefore, byusing the carbon material together with the other anode material, a highenergy density can be obtained and superior cycle characteristics can beobtained. In addition, the carbon material also functions as anelectrical conductor, and thus the carbon material is preferably used.

In addition, as the anode material capable of inserting and extractinglithium, for example, a material that is capable of inserting andextracting lithium, and contains at least one of metal elements andmetalloid elements as an element can be cited. Such an anode material ispreferably used, since a high energy density can be thereby obtained.Such an anode material may be a simple substance, an alloy, or acompound of a metal element or a metalloid element, or may have one ormore phases thereof at least in part. In the application, alloys includean alloy containing one or more metal elements and one or more metalloidelements, in addition to an alloy including two or more metal elements.Further, an alloy in the application may contain a nonmetallic element.The texture thereof includes a solid solution, a eutectic crystal(eutectic mixture), an intermetallic compound, and a texture in whichtwo or more thereof coexist.

As such a metal element or such a metalloid element composing the anodematerial, for example, a metal element or a metalloid element capable offorming an alloy with lithium can be cited. Specifically, magnesium(Mg), boron (B), aluminum, gallium (Ga), indium (In), silicon (Si),germanium (Ge), tin (Sn), lead (Pb), bismuth (Bi), cadmium (Cd), silver(Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium(Pd), platinum (Pt) and the like can be cited. Of the foregoing, atleast one of silicon and tin is particularly preferable. Silicon and tinhave the high ability to insert and extract lithium, and can provide ahigh energy density.

As an anode material containing at least one of silicon and tin, forexample, the simple substance, an alloy, or a compound of silicon; thesimple substance, an alloy, or a compound of tin; or a material havingone or more phases thereof at least in part can be cited. One thereofmay be used singly, or two or more thereof may be used by mixing.

As the alloy of silicon, for example, an alloy containing at least oneselected from the group consisting of tin, nickel, copper, iron, cobalt(Co), manganese (Mn), zinc, indium, silver, titanium (Ti), germanium,bismuth, antimony (Sb), and chromium (Cr) as a second element other thansilicon can be cited. As the alloy of tin, for example, an alloycontaining at least one selected from the group consisting of silicon,nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium,germanium, bismuth, antimony, and chromium as a second element otherthan tin can be cited.

As the compound of silicon or the compound of tin, for example, acompound containing oxygen or carbon can be cited. In addition tosilicon or tin, the compound may contain the foregoing second element.

In particular, as the anode material containing at least one of siliconand tin, for example, an anode material containing a second element anda third element in addition to tin as a first element is alsopreferable. As the second element, at least one selected from the groupconsisting of cobalt, iron, magnesium, titanium, vanadium (V), chromium,manganese, nickel, copper, zinc, gallium, zirconium, niobium (Nb),molybdenum (Mo), silver, indium, cerium (Ce), hafnium, tantalum (Ta),tungsten (W), bismuth, and silicon is used. As the third element, atleast one selected from the group consisting of boron, carbon, aluminum,and phosphorus is used. When the second element and the third elementare contained, the cycle characteristics are improved.

Specially, as an anode material, a CoSnC-containing material thatcontains tin, cobalt, and carbon as an element, in which the carboncontent is in the range from 9.9 wt % to 29.7 wt %, and the cobalt ratioto the total of tin and cobalt (Co/(Sn+Co)) is in the range from 30 wt %to 70 wt % is preferable. In such a composition range, a high energydensity can be obtained, and superior cycle characteristics can beobtained.

The CoSnC-containing material may further contain other elementaccording to needs. As other element, for example, silicon, iron,nickel, chromium, indium, niobium, germanium, titanium, molybdenum,aluminum, phosphorus, gallium, bismuth or the like is preferable. Two ormore thereof may be contained, since thereby the capacity or the cyclecharacteristics can be further improved.

The CoSnC-containing material has a phase containing tin, cobalt, andcarbon. Such a phase preferably has a low crystallinity structure or anamorphous structure. Further, in the CoSnC-containing material, at leastpart of carbon as an element is preferably bonded to a metal element ora metalloid element as other element. It is thought that lowering ofcycle characteristics is caused by cohesion or crystallization of tin orthe like. In this regard, when carbon is bonded to other element, suchcohesion or crystallization can be prevented.

As a measurement method for examining bonding state of elements, forexample, X-ray Photoelectron Spectroscopy (XPS) can be cited. In XPS, inthe case of graphite, the peak of is orbit of carbon (CIs) is observedat 284.5 eV in the apparatus in which energy calibration is made so thatthe peak of 4f orbit of gold atom (Au4f) is obtained in 84.0 eV. In thecase of surface contamination carbon, the peak is observed at 284.8 eV.Meanwhile, in the case of higher electric charge density of carbonelement, for example, when carbon is bonded to a metal element or ametalloid element, the peak of C1s is shown in the region lower than284.5 eV. That is, when the peak of the composite wave of C1s obtainedfor the CoSnC-containing material is observed in the region lower than284.5 eV, at least part of carbon contained in the CoSnC-containingmaterial is bonded to the metal element or the metalloid element asother element.

In XPS, for example, the peak of C1s is used for correcting the energyaxis of spectrums. Since surface contamination carbon generally existson the surface, the peak of C1s of the surface contamination carbon isset to in 284.8 eV, which is used as an energy reference. In XPS, thewaveform of the peak of C1s is obtained as a form including the peak ofthe surface contamination carbon and the peak of carbon in theCoSnC-containing material. Therefore, for example, the waveform isanalyzed by using commercially available software to separate the peakof the surface contamination carbon and the peak of carbon in theCoSnC-containing material. In the analysis of the waveform, the positionof the main peak existing on the lowest bound energy side is set to theenergy reference (284.8 eV).

As the anode material capable of inserting and extracting lithium, forexample, a metal oxide, a polymer compound and the like capable ofinserting and extracting lithium can be cited. As the metal oxide, forexample, iron oxide, ruthenium oxide, molybdenum oxide or the like canbe cited. As the polymer compound, for example, polyacetylene,polyaniline, polypyrrole or the like can be cited.

It is needless to say that a mixture of the foregoing anode materialscapable of inserting and extracting lithium may be used.

As the electrical conductor, for example, a carbon material such asgraphite, carbon black, and Ketjen black can be cited. Such a carbonmaterial may be used singly, or two or more thereof may be used bymixing. The electrical conductor may be a metal material, a conductivepolymer or the like as long as the material has the conductivity.

As the binder, for example, a synthetic rubber such as styrene-butadienerubber, fluorinated rubber, and ethylene propylene diene; or a polymermaterial such as polyvinylidene fluoride can be cited. One thereof maybe used singly, or two or more thereof may be used by mixing. However,when the cathode 21 and the anode 22 are spirally wound as shown in FIG.1, flexible styrene-butadiene rubber, flexible fluorinated rubber or thelike is preferably used.

In the secondary battery, by adjusting the amount of the cathode activematerial and the amount of the anode active material, the chargecapacity of the anode active material becomes larger than the chargecapacity of the cathode active material, so that lithium metal is notprecipitated on the anode 22 even when fully charged.

The separator 23 separates the cathode 21 from the anode 22, and passeslithium ions while preventing current short circuit due to contact ofthe both electrodes. The separator 23 is made of, for example, a porousfilm made of a synthetic resin such as polytetrafluoroethylene,polypropylene, and polyethylene, or a ceramics porous film. Theseparator 23 may have a structure in which two or more porous films asthe foregoing porous films are layered. Specially, a polyolefin porousfilm is preferable since the polyolefin porous film has superior effectfor preventing short circuit, and can contribute to improving batterysafety by the shutdown effect. In particular, polyethylene is preferablesince the shutdown effect can be obtained in the range from 100 deg C.to 160 deg C., and their electrochemical stability is superior.Polypropylene is also preferable. In addition, as long as a resin hasthe chemical stability, the resin may be used by being copolymerized orblended with polyethylene or polypropylene.

The foregoing electrolytic solution as a liquid electrolyte isimpregnated in the separator 23. Thereby, superior storagecharacteristics and the superior cycle characteristics can be obtained.

The secondary battery can be manufactured, for example, as follows.

First, for example, the cathode 21 is formed by forming the cathodeactive material layer 21B on the both faces of the cathode currentcollector 21A. The cathode active material layer 21B is formed asfollows. Cathode active material powder, an electrical conductor, and abinder are mixed to prepare a cathode mixture, which is dispersed in asolvent to obtain paste cathode mixture slurry. Then, the cathodecurrent collector 21A is coated with the cathode mixture slurry, whichis dried, and the resultant is compression-molded. Further, for example,according to a procedure similar to that of the cathode 21, the anode 22is formed by forming the anode active material layer 22B on the bothfaces of the anode current collector 22A.

Subsequently, the cathode lead 25 is attached to the cathode currentcollector 21A by being welded, and the anode lead 26 is attached to theanode current collector 22A by being welded. Subsequently, the cathode21 and the anode 22 are spirally wound with the separator 23 in between,and thereby the spirally wound electrode body 20 is formed. The end ofthe cathode lead 25 is welded to the safety valve mechanism 15, and theend of the anode lead 26 is welded to the battery can 11. After that,the spirally wound electrode body 20 is sandwiched between the pair ofinsulating plates 12 and 13, and contained inside the battery can 11.Subsequently, the electrolytic solution is injected into the battery can11 and impregnated in the separator 23. Finally, at the open end of thebattery can 11, the battery cover 14, the safety valve mechanism 15, andthe PTC device 16 are fixed by being caulked with the gasket 17. Thesecondary battery shown in FIG. 1 and FIG. 2 is thereby completed.

In the secondary battery, when charged, for example, lithium ions areextracted from the cathode 21 and inserted in the anode 22 through theelectrolytic solution. Meanwhile, when discharged, for example, lithiumions are extracted from the anode 22, and inserted in the cathode 21through the electrolytic solution.

According to the secondary battery, in the case that the capacity of theanode 22 is expressed by the capacity component based on insertion andextraction of lithium, the solvent of the electrolytic solution containsthe sulfone compound shown in Chemical formula 1. Thus, thedecomposition reaction of the electrolytic solution is prevented.Therefore, the storage characteristics and the cycle characteristics canbe improved.

Next, a description will be given of a second battery and a thirdbattery. For the elements common to those of the first battery, the samereferential symbols are affixed thereto, and the description thereofwill be omitted.

Second Battery

The second battery has a structure, operations, and effects similar tothose of the first battery except that the anode 22 has a differentstructure, and can be manufactured by a procedure similar to that of thefirst battery.

The anode 22 has a structure in which the anode active material layer22B is provided on the both faces of the anode current collector 22A inthe same manner as in the first battery. The anode active material layer22B contains, for example, an anode active material containing siliconor tin as an element. Specifically, for example, the anode activematerial layer 22B contains the simple substance, an alloy, or acompound of silicon, or the simple substance, an alloy, or a compound oftin. The anode active material layer 22B may contain two or morethereof.

The anode active material layer 22B is formed by using, for example,vapor-phase deposition method, liquid-phase deposition method, sprayingmethod, firing method, or two or more of these methods. The anode activematerial layer 22B and the anode current collector 22A are preferablyalloyed at the interface thereof at least in part. Specifically, it ispreferable that at the interface thereof, the element of the anodecurrent collector 22A is diffused in the anode active material layer22B, or the element of the anode active material layer 22B is diffusedin the anode current collector 22A, or both elements are diffusedtherein each other. Thereby, deconstruction due to expansion andshrinkage of the anode active material layer 22B caused by charge anddischarge can be prevented, and electron conductivity between the anodeactive material layer 22B and the anode current collector 22A can beimproved.

As vapor-phase deposition method, for example, physical depositionmethod or chemical deposition method can be cited. Specifically, vacuumdeposition method, sputtering method, ion plating method, laser ablationmethod, thermal CVD (Chemical Vapor Deposition) method, plasma CVDmethod and the like can be cited. As liquid-phase deposition method, aknown technique such as electrolytic plating and electroless plating canbe used. Firing method is, for example, a method in which a particulateanode active material, a binder and the like are mixed and dispersed ina solvent, and then the anode current collector 22A is coated with themixture, and the resultant is heat-treated at a temperature higher thanthe melting point of the binder and the like. For firing method, a knowntechnique such as atmosphere firing method, reactive firing method, andhot press firing method can be cited.

Third Battery

The third battery is a lithium metal secondary battery in which thecapacity of the anode 22 is expressed by the capacity component based onprecipitation and dissolution of lithium. The secondary battery has astructure similar to that of the first battery, except that the anodeactive material layer 22B is made of lithium metal, and is manufacturedin the same manner as that of the first battery.

In the secondary battery, the lithium metal is used as an anode activematerial. Thereby, a high energy density can be obtained. The anodeactive material layer 22B may exist in assembling. Otherwise, it ispossible that the anode active material layer 22B does not exist inassembling, and is made of the lithium metal precipitated in charging.Otherwise, by using the anode active material layer 22B as a currentcollector, the anode current collector 22A may be omitted.

In the secondary battery, when charged, for example, lithium ions areextracted from the cathode 21, and precipitated as the lithium metal onthe surface of the anode current collector 22A through the electrolyticsolution. Meanwhile, when discharged, for example, the lithium metal iseluted as lithium ions from the anode active material layer 22B, and thelithium ions are inserted in the cathode 21 through the electrolyticsolution.

According to this secondary battery, in the case that the capacity ofthe anode 22 is expressed by the capacity component based onprecipitation and dissolution of lithium, the solvent of theelectrolytic solution contains the sulfone compound shown in Chemicalformula 1. Therefore, the storage characteristics and the cyclecharacteristics can be improved.

Fourth Battery

FIG. 3 shows an exploded perspective structure of a fourth battery. Inthe battery, a spirally wound electrode body 30 on which a cathode lead31 and an anode lead 32 are attached is contained inside a film packagemember 40. The battery structure is a so-called laminated type secondarybattery.

The cathode lead 31 and the anode lead 32 are respectively directed frominside to outside of the package member 40 in the same direction, forexample. The cathode lead 31 is made of, for example, a metal materialsuch as aluminum. The anode lead 32 is made of, for example, a metalmaterial such as copper, nickel, and stainless. The respective metalmaterials composing the cathode lead 31 and the anode lead 32 are in theshape of a thin plate or mesh.

The package member 40 is made of a rectangular aluminum laminated filmin which, for example, a nylon film, an aluminum foil, and apolyethylene film are bonded together in this order. The package member40 is, for example, arranged so that the polyethylene film and thespirally wound electrode body 30 are opposed, and the respective outeredges are contacted to each other by fusion bonding or an adhesive. Anadhesive film 41 to protect from entering of outside air is insertedbetween the package member 40 and the cathode lead 31, the anode lead32. The adhesive film 41 is made of a material having contactcharacteristics to the cathode lead 31 and the anode lead 32, forexample, and is made of a polyolefin resin such as polyethylene,polypropylene, modified polyethylene, and modified polypropylene.

The package member 40 may be made of a laminated film having otherstructure, a polymer film such as polypropylene, or a metal film,instead of the foregoing three-layer aluminum laminated film.

FIG. 4 shows a cross sectional structure taken along line IV-IV of thespirally wound electrode body 30 shown in FIG. 3. In the spirally woundelectrode body 30, a cathode 33 and an anode 34 are layered with aseparator 35 and an electrolyte 36 in between and then spirally wound.The outermost periphery thereof is protected by a protective tape 37.

The cathode 33 has a structure in which a cathode active material layer33B is provided on the both faces of a cathode current collector 33A.The anode 34 has a structure in which an anode active material layer 34Bis provided on the both faces of an anode current collector 34A.Arrangement is made so that the anode active material layer 34B isopposed to the cathode active material layer 33B. The structures of thecathode current collector 33A, the cathode active material layer 33B,the anode current collector 34A, the anode active material layer 34B,and the separator 35 are similar to those of the cathode currentcollector 21A, the cathode active material layer 21B, the anode currentcollector 22A, the anode active material layer 22B, and the separator 23of the foregoing first and second batteries.

The electrolyte 36 is so-called gelatinous, containing the foregoingelectrolytic solution and a polymer compound that holds the electrolyticsolution. The gel electrolyte is preferable, since high ion conductivity(for example, 1 mS/cm or more at room temperature) can be obtained andliquid leakage of the battery can be prevented.

As the polymer compound, for example, polyacrylonitrile, polyvinylidenefluoride, a copolymer of polyvinylidene fluoride andpolyhexafluoropropylene, polytetrafluoroethylene,polyhexafluoropropylene, polyethylene oxide, polypropylene oxide,polyphosphazene, polysiloxane, polyvinyl acetate, polyvinyl alcohol,polymethylmethacrylate, polyacrylic acid, polymethacrylic acid,styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene,polycarbonate or the like can be cited. One of these polymer compoundsmay be used singly, or two or more thereof may be used by mixing. Inparticular, in terms of electrochemical stability, polyacrylonitrile,polyvinylidene fluoride, polyhexafluoropropylene, polyethylene oxide orthe like is preferably used. The addition amount of the polymer compoundin the electrolytic solution varies according to the compatibilitythereof, and for example, is preferably in the range from 5 wt % to 50wt %.

The content of the electrolyte salt is similar to that of the first tothe third batteries. However, in this case, the solvent means a wideconcept including not only the liquid solvent but also a solvent havingion conductivity capable of dissociating the electrolyte salt.Therefore, when the polymer compound having ion conductivity is used,the polymer compound is also included in the solvent.

As the electrolyte 36, instead of the electrolyte in which theelectrolytic solution is held by the polymer compound, the electrolyticsolution may be directly used. In this case, the electrolytic solutionis impregnated in the separator 35.

The secondary battery is manufactured, for example, as follows.

First, a precursor solution containing the electrolytic solution, apolymer compound, and a mixed solvent is prepared. Then, the cathode 33and the anode 34 are respectively coated with the precursor solution.After that, the mixed solvent is volatilized to form the electrolyte 36.Subsequently, the cathode lead 31 is attached to the cathode currentcollector 33A, and the anode lead 32 is attached to the anode currentcollector 34A. Subsequently, the cathode 33 and the anode 34 formed withthe electrolyte 36 are layered with the separator 35 in between toobtain a lamination. After that, the lamination is spirally wound in thelongitudinal direction, the protective tape 37 is adhered to theoutermost periphery thereof to form the spirally wound electrode body30. Subsequently, for example, the spirally wound electrode body 30 issandwiched between the package members 40, and outer edges of thepackage members 40 are contacted by thermal fusion bonding or the liketo enclose the spirally wound electrode body 30. At this time, theadhesive film 41 is inserted between the cathode lead 31/the anode lead32 and the package member 40. Thereby, the secondary battery shown inFIG. 3 and FIG. 4 is completed.

Otherwise, the secondary battery may be manufactured as follows. First,the cathode lead 31 and the anode lead 32 are respectively attached onthe cathode 33 and the anode 34. After that, the cathode 33 and theanode 34 are layered with the separator 35 in between and spirallywound. The protective tape 37 is adhered to the outermost peripherythereof, and a spirally wound body as a precursor of the spirally woundelectrode body 30 is formed. Subsequently, the spirally wound body issandwiched between the package members 40, the peripheral edges otherthan one side are contacted by thermal fusion bonding or the like toobtain a pouched state, and the spirally wound body is contained insidethe pouched-like package member 40. Subsequently, a composition ofmatter for electrolyte containing the electrolytic solution, a monomeras a raw material for a polymer compound, a polymerization initiator,and if necessary other material such as a polymerization inhibitor isprepared, which is injected into the pouched-like package member 40.After that, the opening of the package member 40 is hermetically sealedby, for example, thermal fusion bonding or the like. Finally, themonomer is thermally polymerized to obtain a polymer compound. Thereby,the gel electrolyte 36 is formed. Consequently, the secondary batteryshown in FIG. 3 and FIG. 4 is completed.

The operations and the effects of the secondary battery are similar tothose of the first or the second battery described above.

EXAMPLES

Specific examples of the application will be described in detail.

First, with the use of artificial graphite as an anode active material,the laminated film secondary battery shown in FIG. 3 and FIG. 4 wasfabricated. Then, the secondary battery was fabricated as a lithium ionsecondary battery in which the content of the anode 34 was expressed bythe capacity component based on insertion and extraction of lithium.

Examples 1-1 to 1-4

First, the cathode 33 was formed. That is, lithium carbonate (Li₂CO₃)and cobalt carbonate (COCO₃) were mixed at a molar ratio of 0.5:1. Afterthat, the mixture was fired in the air at 900 deg C. for 5 hours.Thereby, lithium cobalt complex oxide (LiCoO₂) was obtained.Subsequently, 91 parts by weight of the lithium cobalt complex oxide asa cathode active material, 6 parts by weight of graphite as anelectrical conductor, and 3 parts by weight of polyvinylidene fluorideas a binder were mixed to obtain a cathode mixture. After that, thecathode mixture was dispersed in N-methyl-2-pyrrolidone to obtain pastecathode mixture slurry. Finally, the both faces of the cathode currentcollector 33A made of a strip-shaped aluminum foil (being 12 μm thick)were uniformly coated with the cathode mixture slurry, which was dried.After that, the resultant was compression-molded by a roll pressingmachine to form the cathode active material layer 33B. After that, thecathode lead 31 made of aluminum was welded to one end of the cathodecurrent collector 33A.

Subsequently, the anode 34 was formed. That is, 90 parts by weight ofartificial graphite powder as an anode active material and 10 parts byweight of polyvinylidene fluoride as a binder were mixed to obtain ananode mixture. After that, the mixture was dispersed inN-methyl-2-pyrrolidone to obtain paste anode mixture slurry. Finally,the both faces of the anode current collector 34A made of a strip-shapedcopper foil (being 15 μm thick) were uniformly coated with the anodemixture slurry, which was dried. After that, the resultant wascompression-molded by a roll pressing machine to form the anode activematerial layer 34B. After that, the anode lead 32 made of nickel waswelded to one end of the anode current collector 34A.

Subsequently, the cathode 33, the separator 35 made of a micro porouspolypropylene film (being 25 μm thick), and the anode 34 were layered inthis order. After that, the resultant lamination was spirally wound manytimes in the longitudinal direction, the end portion of the spirallywound body was fixed by a protective tape 37 made of an adhesive tape,and thereby a spirally wound body as a precursor of the spirally woundelectrode body 30 was formed. Subsequently, the spirally wound body wasinserted between the package members 40 made of a laminated film havingthree-layer structure (total thickness: 100 μm) in which nylon (being 30μm thick), aluminum (being 40 μm thick), and non-stretched polypropylene(being 30 μm thick) were layered from the outside. After that, the outeredges other than the edge of one side of the package members 40 werethermally fusion-bonded with each other. Thereby, the spirally woundbody was contained inside the package members 40 in a pouched state.Subsequently, the electrolytic solution was injected through the openingof the package member 40, the electrolytic solution as the electrolyte36 was impregnated in the separator 35, and thereby the spirally woundelectrode body 30 was formed.

For the electrolytic solution, a mixture of ethylene carbonate (EC),diethyl carbonate (DEC), and bis(trimethylsilyl)methanedisulfonate shownin Chemical formula 3 as the sulfone compound shown in Chemical formula1 was used as a solvent; and lithium hexafluorophosphate (LiPF₆) wasused as an electrolyte salt. The mixture ratio of EC and DEC wasEC:DEC=30:70 at a weight ratio. The content ofbis(trimethylsilyl)methanedisulfonate in the electrolytic solution was0.01 wt % (Example 1-1), 1 wt % (Example 1-2), 3 wt % (Example 1-3), or5 wt % (Example 1-4). The concentration of lithium hexafluorophosphatein the electrolytic solution was 1 mol/kg.

Finally, the opening of the package member 40 was thermallyfusion-bonded and sealed in the vacuum atmosphere. Thereby, thelaminated film type secondary battery was completed.

Examples 1-5 to 1-11

A procedure was performed in the same manner as that of Example 1-2,except that as a solvent, vinylene carbonate (VC: Example 1-5), vinylethylene carbonate (VEC: Example 1-6), 4-fluoro-1,3-dioxolane-2-one(FEC: Example 1-7), 4,5-difluoro-1,3-dioxolane-2-one (DFEC: Example1-8), propene sultone (PRS: Example 1-9), succinic anhydride (SCAH:Example 1-10), or sulfobenzoic anhydride (SBAH: Example 1-11) wasfurther added. The content of VC or the like in the electrolyticsolution was 1 wt %.

Comparative Example 1-1

A procedure was performed in the same manner as that of Examples 1-1 to1-4, except that bis(trimethylsilyl)methanedisulfonate (Chemical formula3) was not contained in the solvent.

Comparative Example 1-2

A procedure was performed in the same manner as that of Example 1-2,except that bis(methyl)methanedisulfonate shown in Chemical formula 17was contained in the solvent instead ofbis(trimethylsilyl)methanedisulfonate shown in Chemical formula 3.

Comparative Examples 1-3 to 1-5

A procedure was performed in the same manner as that of Examples 1-5,1-7, and 1-8, except that bis(trimethylsilyl)methanedisulfonate(Chemical formula 3) was not contained in the solvent.

When the storage characteristics and the cycle characteristics of thesecondary batteries of Examples 1-1 to 1-11 and Comparative examples 1-1to 1-5 were examined, the results shown in Table 1 were obtained.

In examining the storage characteristics, the secondary battery wasstored by the following procedure, and thereby the discharge capacityretention ratio was calculated. First, charge and discharge wereperformed 2 cycles in the atmosphere of 23 deg C., and thereby thedischarge capacity at the second cycle (discharge capacity beforestorage) was measured. Subsequently, the secondary battery was stored ina constant temperature bath at 60 deg C. for 10 days in a state of beingcharged again. After that, discharge was performed in the atmosphere of23 deg C., and thereby the discharge capacity at the third cycle(discharge capacity after storage) was measured. Finally, the dischargecapacity retention ratio (%)=(discharge capacity after storage/dischargecapacity before storage)×100 was calculated. The charge and dischargecondition of 1 cycle was as follows. That is, after constant current andconstant voltage charge was performed at the charge current of 0.2 Cuntil the upper limit voltage of 4.2 V, constant current discharge wasperformed at the discharge current of 0.2 C until the final voltage of2.5 V. “0.2 C” means the current value at which the theoretical capacityis completely discharged in 5 hours.

In examining the cycle characteristics, the secondary battery wasrepeatedly charged and discharged by the following procedure, andthereby the discharge capacity retention ratio was obtained. First,charge and discharge were performed 2 cycles in the atmosphere of 23 degC., and thereby the discharge capacity at the second cycle was measured.Subsequently, the secondary battery was charged and discharged 50 cyclesin a constant temperature bath at 45 deg C., and thereby the dischargecapacity at the 50th cycle was measured. Finally, the discharge capacityretention ratio (%)=(discharge capacity at the 50th cycle at 45 degC./discharge capacity at the second cycle at 23 deg C.)×100 wascalculated. The charge and discharge condition of 1 cycle was similar tothat of the case examining the storage characteristics.

The foregoing procedures, conditions and the like in examining theforegoing storage characteristics and the foregoing cyclecharacteristics were similar to those in evaluating the samecharacteristics for the following examples and comparative examples.

TABLE 1 Anode active material: artificial graphite Discharge capacityretention Solvent ratio (%) Electrolyte Sulfone compound Storage Cyclesalt Type Type wt % characteristics characteristics Example 1-1 LiPF₆EC + DEC — Chemical 0.01 82 81 Example 1-2 1.0 mol/kg formula 3 1 83 84Example 1-3 3 85 85 Example 1-4 5 85 84 Example 1-5 LiPF₆ EC + DEC VCChemical 1 86 90 1.0 mol/kg 1 wt % formula 3 Example 1-6 VEC 85 88 1 wt% Example 1-7 FEC 86 89 1 wt % Example 1-8 DFEC 88 92 1 wt % Example 1-9PRS 93 84 1 wt % Example 1-10 SCAH 90 85 1 wt % Example 1-11 SBAH 92 861 wt % Comparative LiPF₆ EC + DEC — — — 81 80 example 1-1 1.0 mol/kgComparative — Chemical 1 82 81 example 1-2 formula 17 Comparative VC — —84 84 example 1-3 1 wt % Comparative FEC — — 82 82 example 1-4 1 wt %Comparative DFEC — — 85 85 example 1-5 1 wt %

As shown in Table 1, in Examples 1-1 to 1-4 in which the solventcontained bis(trimethylsilyl)methanedisulfonate, the discharge capacityretention ratios of the storage characteristics and the cyclecharacteristics were higher than those of Comparative example 1-1 inwhich the solvent did not contain bis(trimethylsilyl)methanedisulfonate.The upper limit and the lower limit of the content ofbis(trimethylsilyl)methanedisulfonate in the case that the foregoingresult was obtained in Examples 1-1 to 1-4 were respectively 0.01 wt %and 5 wt %. Further, in Example 1-2 in which the solvent containedbis(trimethylsilyl)methanedisulfonate, the discharge capacity retentionratios of the storage characteristics and the cycle characteristics werehigher than those of in Comparative example 1-2 in which the solventcontained bis(methyl)methanedisulfonate instead ofbis(trimethylsilyl)methanedisulfonate. This result showed the followingfact. That is, bis(trimethylsilyl)methanedisulfonate andbis(methyl)methanedisulfonate commonly have 2 sulfonyl groups. However,to improve the discharge capacity retention ratios of the storagecharacteristics and the cycle characteristics,bis(trimethylsilyl)methanedisulfonate is more advantageous thanbis(methyl)methanedisulfonate. Consequently, it was confirmed that inthe secondary battery in which the anode active material containedartificial graphite, when the solvent of the electrolytic solutioncontained the sulfone compound shown in Chemical formula 1, the storagecharacteristics and the cycle characteristics were improved. It was alsoconfirmed that in this case, the content of the sulfone compound shownin Chemical formula 1 in the electrolytic solution was preferably in therange from 0.01 wt % to 5 wt %.

In Examples 1-5 to 1-11 in which the solvent contained VC, VEC, FEC,DFEC, PRS, SCAH, or SBAH, the discharge capacity retention ratio of thestorage characteristics was higher than that of Comparative example 1-2in which the solvent did not contained VC, VEC, FEC, DFEC, PRS, SCAH, orSBAH, and the discharge capacity retention ratio of the cyclecharacteristics was equal to or more than that of Example 1-2. It isneedless to say that in the case that when the solvent contained VC,FEC, or DFEC, in Examples 1-5, 1-7, and 1-8 in which the solventcontained bis(trimethylsilyl)methanedisulfonate, the discharge capacityretention ratios of the storage characteristics and the cyclecharacteristics were higher than those of Comparative examples 1-3 to1-5 in which the solvent did not containbis(trimethylsilyl)methanedisulfonate. Accordingly, it was confirmedthat in the secondary battery in which the solvent of the electrolyticsolution contained the sulfone compound shown in Chemical formula 1,when the solvent contained the cyclic ester carbonate having anunsaturated bond, the cyclic ester carbonate having a halogen as anelement shown in Chemical formula 5, sultone, or acid anhydride, highereffects could be obtained. No examples have been herein disclosed for acase that the solvent contained the chain ester carbonate having ahalogen as an element shown in Chemical formula 4. However, in terms ofpreventing decomposition of the electrolytic solution, the chain estercarbonate having a halogen as an element shown in Chemical formula 4 hasproperty similar to those of the cyclic ester carbonate having a halogenas an element shown in Chemical formula 5. Therefore, it is evident thatin the case using the chain ester carbonate having a halogen as anelement shown in Chemical formula 4, the foregoing effects can beobtained.

In this case, in particular, when comparison between the respectivedischarge capacity retention ratios of the storage characteristics andthe cycle characteristics was made based on every added solvent type,the following results were obtained. That is, for the cyclic estercarbonate having an unsaturated bond, the discharge capacity retentionratios in Example 1-5 containing VC were higher than those of Example1-6 containing VEC. For the cyclic ester carbonate having a halogen asan element shown in Chemical formula 5, the discharge capacity retentionratios in Example 1-8 containing DFEC were higher than those of Example1-7 containing FEC. For the acid anhydride, the discharge capacityretention ratios in Example 1-11 containing SBAH were higher than thoseof Example 1-10 containing SCAH. Accordingly, it was confirmed that VCwas more preferably contained than VEC as the cyclic ester carbonatehaving an unsaturated bond, DFEC was more preferably contained than FECas the cyclic ester carbonate having a halogen as an element shown inChemical formula 5, and SBAH was more preferably contained than SCAH asthe acid anhydride.

Examples 2-1 to 2-4

A procedure was performed in the same manner as that of Example 1-2,except that as an electrolyte salt, lithium tetrafluoroborate (LiBF₄:Example 2-1), bis[oxalate-O,O′]lithium borate in Chemical formula 11(6)(Example 2-2), [bis(3,3,3-trifluoromethyl)glycolate oxalate]lithiumborate in Chemical formula 12(2) (Example 2-3), or lithium1,3-perfluoropropanedisulfonylimide in Chemical formula 16(2) (Example2-4) was further added. The concentration of lithium hexafluorophosphatein the electrolytic solution was 0.9 mol/kg, and the concentration oflithium tetrafluoroborate or the like in the electrolytic solution was0.1 mol/kg.

Example 2-5

A procedure was performed in the same manner as that of Example 1-2,except that as an electrolyte salt, bis[oxalate-O,O′]lithium borate inChemical formula 11(6) and lithium 1,3-perfluoropropanedisulfonylimidein Chemical formula 16(2) were further added. The concentration oflithium hexafluorophosphate in the electrolytic solution was 0.8 mol/kg,and the concentrations of bis[oxalate-O,O′]lithium borate and lithium1,3-perfluoropropanedisulfonylimide were respectively 0.1 mol/kg.

Comparative Example 2

A procedure was performed in the same manner as that of Example 2-2,except that bis(trimethylsilyl)methanedisulfonate was not contained inthe solvent.

For the secondary batteries of Examples 2-1 to 2-5 and Comparativeexample 2, the storage characteristics and the cycle characteristicswere examined. The results shown in Table 2 were obtained. Table 2 alsoshows respective characteristics of Example 1-2 and Comparative example1-1.

TABLE 2 Anode active material: artificial graphite Discharge capacityretention Solvent ratio (%) Sulfone compound Storage Cycle Electrolytesalt Type Type wt % characteristics characteristics Example 1-2 LiPF₆EC + DEC Chemical 1 83 84 1.0 mol/kg formula 3 Example 2-1 LiPF₆ LiBF₄85 84 0.9 mol/kg 0.1 mol/kg Example 2-2 Chemical formula 11(6) 85 88 0.1mol/kg Example 2-3 Chemical formula 12(2) 86 90 0.1 mol/kg Example 2-4Chemical formula 16(2) 88 86 0.1 mol/kg Example 2-5 LiPF₆ ChemicalChemical 89 90 0.8 mol/kg formula formula 11(6) 16(2) 0.1 mol/kg 0.1mol/kg Comparative LiPF₆ EC + DEC — — 81 80 Example 1-1 1.0 mol/kgComparative LiPF₆ Chemical formula 11(6) 84 82 example 2 0.9 mol/kg 0.1mol/kg

As shown in Table 2, in Examples 2-1 to 2-5 in which the solventcontained bis(trimethylsilyl)methanedisulfonate, and the electrolytesalt contained lithium tetrafluoroborate, bis[oxalate-O,O′]lithiumborate, [bis(3,3,3-trifluoromethyl)glycolate oxalate]lithium borate, orlithium 1,3-perfluoropropanedisulfonylimide, the discharge capacityretention ratios of the storage characteristics and the cyclecharacteristics were higher than those of Comparative example 1-1 inwhich the solvent did not contain bis(trimethylsilyl)methanedisulfonateand the electrolyte salt did not contain lithium tetrafluoroborate,bis[oxalate-O,O′]lithium borate, [bis(3,3,3-trifluoromethyl)glycolateoxalate]lithium borate, or lithium 1,3-perfluoropropanedisulfonylimide.In Examples 2-1 to 2-5, the discharge capacity retention ratio of thestorage characteristics was higher than that of Example 1-2 in which theelectrolyte salt did not contain the foregoing lithium tetrafluoroborateand the like, and the discharge capacity retention ratio of the cyclecharacteristics was equal to or more than that of Comparative example1-2. It is needless to say that in the case that the electrolyte saltcontained bis[oxalate-O,O′]lithium borate, in Example 2-2 in which thesolvent contained bis(trimethylsilyl)methanedisulfonate, the dischargecapacity retention ratios of the storage characteristics and the cyclecharacteristics were higher than those of Comparative examples 2 inwhich the solvent did not contain bis(trimethylsilyl)methanedisulfonate.Thereby, it was confirmed that in the secondary battery in which thesolvent of the electrolytic solution contained the sulfone compoundshown in Chemical formula 1, when the electrolyte salt contained otherelectrolyte salt together with lithium hexafluorophosphate, the storagecharacteristics and the cycle characteristics were more improved.

In this case, in particular, focusing attention on the number of typesof added electrolyte salts, in Example 2-5 in which 2 types of otherelectrolyte salts were added, the discharge capacity retention ratios ofthe storage characteristics and the cycle characteristics were higherthan those in Examples 2-1 to 2-4 in which one type of other electrolytesalt was added. Accordingly, it was confirmed that two or more types ofother electrolyte salts were preferably added in order to more improvethe storage characteristics and the cycle characteristics.

Next, by using silicon as the anode active material, the laminated filmtype secondary battery shown in FIG. 3 and FIG. 4 was fabricated. Atthat time, the secondary battery was fabricated as a lithium ionsecondary battery in which the capacity of the anode 34 was expressed bythe capacity component based on insertion and extraction of lithium.

Examples 3-1 to 3-11

A procedure was performed in the same manner as that of Examples 1-1 to1-11, except that the procedure for forming the anode 34 was differentfrom that of Examples 1-1 to 1-11. When the anode 34 was formed, theanode active material layer 34B made of silicon was formed on the anodecurrent collector 34A made of a copper foil (being 15 μm thick) byelectron beam evaporation method.

Comparative Examples 3-1 to 3-5

A procedure was performed in the same manner as that of Comparativeexamples 1-1 to 1-5, except that the anode 34 was formed by theprocedure similar to that of Examples 3-1 to 3-11.

For the secondary batteries of Examples 3-1 to 3-11 and Comparativeexamples 3-1 to 3-5, the storage characteristics and the cyclecharacteristics were examined. The results shown in Table 3 wereobtained.

TABLE 3 Anode active material: silicon Discharge capacity retentionSolvent ratio (%) Electrolyte Sulfone compound Storage Cycle salt TypeType wt % characteristics characteristics Example 3-1 LiPF₆ EC + DEC —Chemical 0.01 72 40 Example 3-2 1.0 mol/kg formula 3 1 75 58 Example 3-33 75 62 Example 3-4 5 75 60 Example 3-5 LiPF₆ EC + DEC VC Chemical 1 7870 1.0 mol/kg 1 wt % formula 3 Example 3-6 VEC 76 68 1 wt % Example 3-7FEC 77 64 1 wt % Example 3-8 DFEC 82 78 1 wt % Example 3-9 PRS 91 62 1wt % Example 3-10 SCAH 88 64 1 wt % Example 3-11 SBAH 90 64 1 wt %Comparative LiPF₆ EC + DEC — — — 70 30 Example 3-1 1.0 mol/kg Example3-2 — Chemical 1 72 38 formula 17 Example 3-3 VC — — 75 62 1 wt %Example 3-4 FEC — — 72 55 1 wt % Example 3-5 DFEC — — 80 72 1 wt %

As shown in Table 3, when silicon was used as the anode active material,results almost similar to the results shown in Table 1 in the case ofusing artificial graphite were obtained.

That is, in Examples 3-1 to 3-4 in which the solvent containedbis(trimethylsilyl)methanedisulfonate, when the lower limit and theupper limit of the content of bis(trimethylsilyl)methanedisulfonate inthe electrolytic solution were respectively 0.01 wt % and 5 wt %, thedischarge capacity retention ratios of the storage characteristics andthe cycle characteristics were higher than those in Comparative examples3-1 and 3-2 in which the solvent did not containbis(trimethylsilyl)methanedisulfonate. Accordingly, it was confirmedthat in the secondary battery in which the anode active materialcontained silicon, when the solvent of the electrolytic solutioncontained the sulfone compound shown in Chemical formula 1, the storagecharacteristics and the cycle characteristics were improved. Inaddition, it was confirmed that in the secondary battery in which theanode active material contained silicon, the content of the sulfonecompound shown in Chemical formula 1 in the electrolytic solution waspreferably in the range from 0.01 wt % to 5 wt %.

In Examples 3-5 to 3-11 in which the solvent contained VC or the like,the discharge capacity retention ratios of the storage characteristicsand the cycle characteristics were higher than those in Example 3-2 inwhich the solvent did not contain VC or the like. It is needless to saythat in Examples 3-5 to 3-11 in which the solvent containedbis(trimethylsilyl)methanedisulfonate, the discharge capacity retentionratios of the storage characteristics and the cycle characteristics werehigher than those in Comparative examples 3-1 and 3-2 in which thesolvent did not contain bis(trimethylsilyl)methanedisulfonate. When thesolvent contained VC, FEC, or DFEC, in Examples 3-5, 3-7, and 3-8 inwhich the solvent contained bis(trimethylsilyl)methanedisulfonate, thedischarge capacity retention ratios of the storage characteristics andthe cycle characteristics were higher than those in Comparative examples3-3 to 3-5 in which the solvent did not contain bis(trimethylsilyl)methanedisulfonate. Accordingly, it was confirmed thatin the secondary battery in which the solvent of the electrolyticsolution contained the sulfone compound shown in Chemical formula 1,higher effects could be obtained when the solvent contained the cyclicester carbonate having an unsaturated bond, the cyclic ester carbonatehaving a halogen as an element shown in Chemical formula 5, sultone, oracid anhydride.

In this case, in particular, for the cyclic ester carbonate having anunsaturated bond, the discharge capacity retention ratios of the storagecharacteristics and the cycle characteristics in Example 3-5 containingVC were higher than those of Example 3-6 containing VEC. For the cyclicester carbonate having a halogen as an element shown in Chemical formula5, the discharge capacity retention ratios of the storagecharacteristics and the cycle characteristics in Example 3-8 containingDFEC were higher than those of Example 3-7 containing FEC. For the acidanhydride, the discharge capacity retention ratios of the storagecharacteristics and the cycle characteristics in Example 3-11 containingSBAH were higher than those of Example 3-10 containing SCAH.Accordingly, to improve the storage characteristics and the cyclecharacteristics, it was confirmed that VC was more preferable than VECas the cyclic ester carbonate having an unsaturated bond, DFEC was morepreferable than FEC as the cyclic ester carbonate having a halogen as anelement shown in Chemical formula 5, and SBAH was more preferable thanSCAH as the acid anhydride.

Examples 4-1 to 4-5

A procedure was performed in the same manner as that of Examples 2-1 to2-5, except that the anode 34 was formed by the procedure similar tothat of Examples 3-1 to 3-11.

Comparative Example 4

A procedure was performed in the same manner as that of Example 4-2,except that the anode 34 was formed by the procedure similar to that ofExamples 3-1 to 3-11, and bis(trimethylsilyl)methanedisulfonate was notcontained in the solvent.

For the secondary batteries of Examples 4-1 to 4-5 and Comparativeexample 4, the storage characteristics and the cycle characteristicswere examined. The results shown in Table 4 were obtained. Table 4 alsoshows respective characteristics of Example 3-2 and Comparative example3-1

TABLE 4 Anode active material: silicon Discharge capacity retentionSolvent ratio (%) Sulfone compound Storage Cycle Electrolyte salt TypeType wt % characteristics characteristics Example 3-2 LiPF₆ EC + DECChemical 1 75 58 1.0 mol/kg formula 3 Example 4-1 LiPF₆ LiBF₄ 80 62 0.9mol/kg 0.1 mol/kg Example 4-2 Chemical formula 11(6) 80 70 0.1 mol/kgExample 4-3 Chemical formula 12(2) 82 74 0.1 mol/kg Example 4-4 Chemicalformula 16(2) 84 64 0.1 mol/kg Example 4-5 LiPF₆ Chemical Chemical 85 720.8 mol/kg formula formula 11(6) 16(2) 0.1 mol/kg 0.1 mol/kg ComparativeLiPF₆ EC + DEC — — 70 30 example 3-1 1.0 mol/kg Comparative LiPF₆Chemical formula 11(6) 75 62 example 4 0.9 mol/kg 0.1 mol/kg

As shown in Table 4, when silicon was used as the anode active material,results almost similar to the results shown in Table 2 in the case ofusing artificial graphite were obtained.

That is, in Examples 4-1 to 4-5 in which the solvent containedbis(trimethylsilyl)methanedisulfonate and the electrolyte salt containedlithium tetrafluoroborate or the like, the discharge capacity retentionratios of the storage characteristics and the cycle characteristics werehigher than those in Comparative example 3-1 in which the solvent didnot contain bis(trimethylsilyl)methanedisulfonate and the electrolytesalt did not contain lithium tetrafluoroborate or the like. In Examples4-1 to 4-5, the discharge capacity retention ratios of the storagecharacteristics and the cycle characteristics were higher than those inExample 3-2 in which the electrolyte salt did not contain the foregoinglithium tetrafluoroborate or the like. It is needless to say that whenthe electrolyte salt contained bis[oxalate-O,O′]lithium borate, inExample 4-2 in which the solvent containedbis(trimethylsilyl)methanedisulfonate, the discharge capacity retentionratios of the storage characteristics and the cycle characteristics werehigher than those in Comparative example 4 in which the solvent did notcontain bis(trimethylsilyl)methanedisulfonate. Accordingly, it wasconfirmed that in the secondary battery in which the solvent of theelectrolytic solution contained the sulfone compound shown in Chemicalformula 1, the storage characteristics and the cycle characteristicswere more improved when the electrolyte salt contained other electrolytesalt together with lithium hexafluorophosphate.

In this case, in particular, in Example 4-5 in which 2 types of otherelectrolyte salts were added, the discharge capacity retention ratios ofthe storage characteristics and the cycle characteristics were higherthan those in Examples 4-1 to 4-4 in which one type of other electrolytesalt was added. Accordingly, it was confirmed that two or more types ofother electrolyte salts were preferably added in order to furtherimprove the storage characteristics and the cycle characteristics.

As evidenced by the foregoing results of Table 1 to Table 4, it wasconfirmed that when the solvent of the electrolytic solution containedthe sulfone compound shown in Chemical formula 1, the storagecharacteristics and the cycle characteristics were improved regardlessof the material used as an anode active material. In particular, it wasfound that higher effects could be obtained when silicon providing ahigh energy density was used as an anode active material, since therebythe increase rate of the discharge capacity retention ratios of thestorage characteristics and the cycle characteristics were improved. Thereason thereof may be as follows. When silicon providing a high energydensity or the like was used as an anode active material, thedecomposition reaction of the electrolytic solution in the anode 34 waseasily generated than in the case of using a carbon material. Thus, whenthe solvent contained the sulfone compound shown in Chemical formula 1in this case, the decomposition inhibition effects of the electrolyticsolution was significantly demonstrated.

The present application has been described with reference to theembodiment and the examples. However, the present application is notlimited to the aspects described in the foregoing embodiment and theforegoing examples, and various modifications may be made. For example,usage applications of the electrolytic solution of the application arenot limited to the battery, but may include other electrochemicaldevices other than the battery. As other applications, for example, acapacitor and the like can be cited.

In the foregoing embodiment and the foregoing examples, the descriptionhas been given of the case using the electrolytic solution or the caseusing the gel electrolyte in which the electrolytic solution is held bythe polymer compound as the electrolyte of the battery of an embodiment.However, other types of electrolyte may be used. As other electrolyte,for example, a mixture of an ion conductive inorganic compound such asion conductive ceramics, ion conductive glass, and ionic crystal and anelectrolytic solution; a mixture of other inorganic compound and anelectrolytic solution; a mixture of the foregoing inorganic compound anda gel electrolyte or the like can be cited.

In the foregoing embodiment and the foregoing examples, the descriptionhas been given of the lithium ion secondary battery in which the anodecapacity is expressed by the capacity component based on insertion andextraction of lithium, or the lithium metal secondary battery in whichthe lithium metal is used as an anode active material and the anodecapacity is expressed by the capacity component based on precipitationand dissolution of lithium as the battery of an embodiment. However, thebattery of an embodiment is not limited thereto. The present applicationcan be similarly applied to a secondary battery in which the anodecapacity includes the capacity component based on insertion andextraction of lithium and the capacity component based on precipitationand dissolution of lithium, and the anode capacity is expressed by thesum of these capacity components, by setting the charge capacity of theanode material capable of inserting and extracting lithium to a smallervalue than that of the charge capacity of the cathode.

Further, in the foregoing embodiment and the foregoing examples, thedescription has been given of the case using lithium as an electrodereactant. However, as an electrode reactant, other Group 1A element suchas sodium (Na) and potassium (K), a Group 2A element such as magnesiumand calcium (Ca), or other light metal such as aluminum may be used. Inthis case, the anode material described in the foregoing embodiment canbe used as an anode active material as well.

Further, in the foregoing embodiment and the foregoing examples, adescription has been given with the specific examples of the cylindricalor laminated film type secondary battery as a battery structure of thebattery of an embodiment. However, the battery of an embodiment can besimilarly applied to a secondary battery having other shape such as acoin type battery, a button type battery, and a square battery, or asecondary battery having other structure such as a lamination structure.Further, the battery of an embodiment can be applied to other batteriessuch as primary batteries in addition to the secondary batteries.

Further, in the foregoing embodiment and the foregoing examples,regarding the content of the sulfone compound shown in Chemical formula1 in the electrolytic solution of the application, the appropriateranges thereof derived from the results of the examples have beendescribed. However, such a description does not totally eliminate thepossibility that the content may be out of the foregoing ranges. Thatis, the foregoing appropriate ranges are ranges particularly preferablefor obtaining the effects of the present application. Therefore, as longas effects of the present application can be obtained, the content maybe out of the foregoing ranges in some degrees.

It should be understood that various changes and modifications to thepresently preferred embodiments described herein will be apparent tothose skilled in the art. Such changes and modifications can be madewithout departing from the spirit and scope of the present subjectmatter and without diminishing its intended advantages. It is thereforeintended that such changes and modifications be covered by the appendedclaims.

1. An electrolytic solution comprising: a solvent containing a sulfone compound shown in Chemical formula 1; and an electrolyte salt:

where R11 represents an a-valence group composed of carbon and an element selected from the group consisting of hydrogen, oxygen, and halogen, where the carbon atom thereof is bonded to a sulfur atom in a sulfonyl group, where R12, R13, and R14 are an alkyl group with the carbon number in a range from 1 to 4, an alkylene group with a carbon number in a range from 1 to 4, or an aryl group, where R12, R13, and R14 are identical or different, and where a represents one of integer numbers 2 or more.
 2. The electrolytic solution according to claim 1, wherein the sulfone compound includes a sulfone compound shown in Chemical formula 2:

where R21 represents a bivalent group composed of carbon and an element selected from the group consisting of hydrogen, oxygen, and halogen, where the carbon atom thereof is bonded to a sulfur atom in a sulfonyl group, where R22, R23, and R24 are an alkyl group with a carbon number in a range from 1 to 4, an alkylene group with the carbon number in a range from 1 to 4, or an aryl group, and where R22, R23, and R24 are identical or different.
 3. The electrolytic solution according to claim 1, wherein a content of the sulfone compound is in a range from 0.01 wt % to 5 wt %.
 4. The electrolytic solution according to claim 1, wherein the solvent contains cyclic ester carbonate having an unsaturated bond.
 5. The electrolytic solution according to claim 1, wherein the solvent contains at least one selected from the group consisting of chain ester carbonate having a halogen as an element shown in Chemical formula 3 and cyclic ester carbonate having a halogen as an element shown in Chemical formula 4:

where R31 to R36 represent a hydrogen group, a halogen group, an alkyl group, or an alkyl halide group, where R31 to R36 are identical or different, and where at least one of R31 to R36 is the halogen group or the alkyl halide group:

where R41 to R44 represent a hydrogen group, a halogen group, an alkyl group, or an alkyl halide group, where R41 to R44 are identical or different, and where at least one of R41 to R44 is the halogen group or the alkyl halide group.
 6. The electrolytic solution according to claim 5, wherein the cyclic ester carbonate having a halogen as an element includes at least one of 4-fluoro-1,3-dioxolane-2-one and 4,5-difluoro-1,3-dioxolane-2-one.
 7. The electrolytic solution according to claim 1, wherein the solvent contains sultone.
 8. The electrolytic solution according to claim 1, wherein the solvent contains an acid anhydride.
 9. The electrolytic solution according to claim 1, wherein the electrolyte salt contains at least one selected from the group consisting of compounds shown in Chemical formula 5, Chemical formula 6, and Chemical formula 7:

where X51 represents a Group 1A element or a Group 2A element in the short period periodic table or aluminum, where M51 represents a transition metal, a Group 3B element, a Group 4B element, or a Group 5B element in the short period periodic table, where R51 represents a halogen group, where Y51 represents —OC—R52-CO—, —OC—CR53₂—, or —OC—CO—, where R52 represents an alkylene group, an alkylene halide group, an arylene group, or an arylene halide group, where R53 represents an alkyl group, an alkyl halide group, an aryl group, or an aryl halide group, and are identical or different, and where a5 represents one of integer numbers 1 to 4, b5 represents 0 or an integer number of 2 or 4, c5, d5, m5, and n5 represent one of integer numbers 1 to 3:

where X61 represents a Group 1A element or a Group 2A element in the short period periodic table, where M61 represents a transition metal, a Group 3B element, a Group 4B element, or a Group 5B element in the short period periodic table, where Y61 represents —OC—(CR61₂)_(b6)—CO—, —R63₂C—(CR62₂)_(c6)—CO—, —R63₂C—(CR62₂)_(c6)—CR63₂—, —R63₂C—(CR62₂)_(c6)—SO₂—, —O₂S—(CR62₂)_(d6)—SO₂—, or —OC—(CR62₂)_(d6)—SO₂—, where R61 and R63 represent a hydrogen group, an alkyl group, a halogen group, or an alkyl halide group, where R61 and R63 are respectively identical or different, where at least one of R61 and R63 is respectively the halogen group or the alkyl halide group, where R62 represents a hydrogen group, an alkyl group, a halogen group, or an alkyl halide group, and are identical or different, where a6, e6, and n6 represent an integer number of 1 or 2, where b6 and d6 represent one of integer numbers 1 to 4, where c6 represents 0 or one of integer numbers 1 to 4, and where f6 and m6 represent one of integer numbers 1 to 3:

where X71 represents a Group 1A element or a Group 2A element in the short period periodic table, where M71 represents a transition metal, a Group 3B element, a Group 4B element, or a Group 5B element in the short period periodic table, where Rf represents a fluorinated alkyl group with the carbon number in the range from 1 to 10 or a fluorinated aryl group with the carbon number in the range from 1 to 10, where Y71 represents —OC—(CR71₂)_(d7)—CO—, —R72₂C—(CR71₂)_(d7)—CO—, —R72₂C—(CR71₂)_(d7)—CR72₂—, —R72₂C—(CR71₂)_(d7)—SO₂—, —O₂S—(CR71₂)_(e7)—SO₂—, or —OC—(CR71₂)_(e7)—SO₂—, where R71 represents a hydrogen group, an alkyl group, a halogen group, or an alkyl halide group, and may be identical or different, where R72 represents a hydrogen group, an alkyl group, a halogen group, or an alkyl halide group, are identical or different, where at least one thereof is the halogen group or the alkyl halide group, where a7, f7, and n7 represent an integer number of 1 or 2, where b7 c7, and e7 represent one of integer numbers 1 to 4, where d7 represents 0 or one of integer numbers 1 to 4, and where g7 and m7 represent one of integer numbers 1 to
 3. 10. The electrolytic solution according to claim 9, wherein: the compound shown in Chemical formula 5 includes at least one selected from the group consisting of difluoro[oxalate-O,O′]lithium borate in Chemical formula 8(1), difluorobis[oxalate-O,O′]lithium phosphate in Chemical formula 8(2), difluoro[3,3,3-trifluoro-2-oxide-2-trifluoromethyl propionate(2-)-O,O′]lithium borate in Chemical formula 8(3), bis[3,3,3-trifluoro-2-oxide-2-trifluoromethyl propionate(2-)-O,O′]lithium borate in Chemical formula 8(4), tetrafluoro[oxalate-O,O′]lithium phosphate in Chemical formula 8(5), and bis[oxalate-O,O′]lithium borate in Chemical formula 8(6); the compound shown in Chemical formula 6 includes at least one selected from the group consisting of (2,2-difluoromalonate oxalate)lithium borate in Chemical formula 9(1), [bis(3,3,3-trifluoromethyl)glycolate oxalate]lithium borate in Chemical formula 9(2), (3,3,3-trifluoromethyl propionate oxalate)lithium borate in Chemical formula 9(3), (2-trifluoromethyl propionate oxalate)lithium borate in Chemical formula 9(4), (4,4,4-trifluoro-3-trifluoromethyl butyric acid oxalate)lithium borate in Chemical formula 9(5), (perfluoropinacolate oxalate)lithium borate in Chemical formula 9(6), (4,4,4-trifluoro-3-methyl butyric acid oxalate)lithium borate in Chemical formula 9(7), and (4,4,4-trifluoro butyric acid oxalate)lithium borate in Chemical formula 9(8); and the compound shown in Chemical formula 7 includes fluorotrifluoromethyl[oxalate-O,O′]lithium borate in Chemical formula 9(9):


11. The electrolytic solution according to claim 1, wherein the electrolyte salt contains at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, and compounds shown in Chemical formula 10, Chemical formula 11, and Chemical formula 12: LiN(C_(m)F_(2m+1)SO₂)(C_(n)F_(2n+1)SO₂)  Chemical formula 10 where m and n represent an integer number of 1 or more, and where m and n are identical or different:

where R81 represents a straight chain or branched perfluoro alkylene group with a carbon number in a range from 2 to 4: LiC(C_(p)F_(2p+1)SO₂)(C_(q)F_(2q+1)SO₂)(C_(r)F_(2r+1)SO₂)  Chemical formula 12 where p, q, and r represent an integer number of 1 or more, and where p, q, and r are identical or different.
 12. A battery comprising: a cathode; an anode; and an electrolytic solution, wherein the electrolytic solution contains a solvent containing a sulfone compound shown in Chemical formula 13 and an electrolyte salt:

where R11 represents an a-valence group composed of carbon and an element selected from the group consisting of hydrogen, oxygen, and halogen, where the carbon atom thereof is bonded to a sulfur atom in a sulfonyl group, where R12, R13, and R14 are an alkyl group with a carbon number in a range from 1 to 4, an alkylene group with the carbon number in the range from 1 to 4, or an aryl group, where R12, R13, and R14 are identical or different, and where a represents one of integer numbers 2 or more.
 13. The battery according to claim 12, wherein the sulfone compound includes a sulfone compound shown in Chemical formula 14:

where R21 represents a bivalent group composed of carbon and an element selected from the group consisting of hydrogen, oxygen, and halogen, where the carbon atom thereof is bonded to a sulfur atom in a sulfonyl group, where R22, R23, and R24 are an alkyl group with the carbon number in a range from 1 to 4, an alkylene group with the carbon number in a range from 1 to 4, or an aryl group, and where R22, R23, and R24 are identical or different.
 14. The battery according to claim 12, wherein a content of the sulfone compound in the electrolytic solution is in a range from 0.01 wt % to 5 wt %.
 15. The battery according to claim 12, wherein the solvent contains cyclic ester carbonate having an unsaturated bond.
 16. The battery according to claim 12, wherein the solvent contains at least one selected from the group consisting of chain ester carbonate having a halogen as an element shown in Chemical formula 15 and cyclic ester carbonate having a halogen as an element shown in Chemical formula 16:

where R31 to R36 represent a hydrogen group, a halogen group, an alkyl group, or an alkyl halide group, where R31 to R36 are identical or different, and where at least one of R31 to R36 is the halogen group or the alkyl halide group:

where R41 to R44 represent a hydrogen group, a halogen group, an alkyl group, or an alkyl halide group, where R41 to R44 are identical or different, where at least one of R41 to R44 is the halogen group or the alkyl halide group.
 17. The battery according to claim 16, wherein the cyclic ester carbonate having a halogen as an element includes at least one of 4-fluoro-1,3-dioxolane-2-one and 4,5-difluoro-1,3-dioxolane-2-one.
 18. The battery according to claim 12, wherein the solvent contains sultone.
 19. The battery according to claim 12, wherein the solvent contains an acid anhydride.
 20. The battery according to claim 12, wherein the electrolyte salt contains at least one selected from the group consisting of compounds shown in Chemical formula 17, Chemical formula 18, and Chemical formula 19:

where X51 represents a Group 1A element or a Group 2A element in the short period periodic table or aluminum (Al), where M51 represents a transition metal, a Group 3B element, a Group 4B element, or a Group 5B element in the short period periodic table, where R51 represents a halogen group, where Y51 represents —OC—R52-CO—, —OC—CR53₂—, or —OC—CO—, where R52 represents an alkylene group, an alkylene halide group, an arylene group, or an arylene halide group, where R53 represents an alkyl group, an alkyl halide group, an aryl group, or an aryl halide group, and are identical or different, where a5 represents one of integer numbers 1 to 4, where b5 represents 0 or an integer number of 2 or 4, where c5, d5, m5, and n5 represent one of integer numbers 1 to 3:

where X61 represents a Group 1A element or a Group 2A element in the short period periodic table, where M61 represents a transition metal, a Group 3B element, a Group 4B element, or a Group 5B element in the short period periodic table, where Y61 represents —OC—(CR61₂)_(b6)—CO—, —R63₂C—(CR62₂)_(c6)—CO—, —R63₂C—(CR62₂)_(c6)—CR63₂—, —R63₂C—(CR62₂)_(c6)—SO₂—, —O₂S—(CR62₂)_(d6)—SO₂—, or —OC—(CR62₂)_(d6)—SO₂—, where R61 and R63 represent a hydrogen group, an alkyl group, a halogen group, or an alkyl halide group, where R61 and R63 are respectively identical or different, where at least one of R61 and R63 is respectively the halogen group or the alkyl halide group, where R62 represents a hydrogen group, an alkyl group, a halogen group, or an alkyl halide group, and are identical or different, where a6, e6, and n6 represent an integer number of 1 or 2, where b6 and d6 represent one of integer numbers 1 to 4, where c6 represents 0 or one of integer numbers 1 to 4, and where f6 and m6 represent one of integer numbers 1 to 3:

where X71 represents a Group 1A element or a Group 2A element in the short period periodic table, where M71 represents a transition metal, a Group 3B element, a Group 4B element, or a Group 5B element in the short period periodic table, where Rf represents a fluorinated alkyl group with the carbon number in the range from 1 to 10 or a fluorinated aryl group with the carbon number in the range from 1 to 10, where Y71 represents —OC—(CR71₂)_(d7)—CO—, —R72₂C—(CR71₂)_(d7)—CO—, —R72₂C—(CR71₂)_(d7)—CR72₂—, —R72₂C—(CR71₂)_(d7)—SO₂—, —O₂S—(CR71₂)_(e7)—SO₂—, or —OC—(CR71₂)_(e7)—SO₂—, where R71 represents a hydrogen group, an alkyl group, a halogen group, or an alkyl halide group, and are identical or different, where R72 represents a hydrogen group, an alkyl group, a halogen group, or an alkyl halide group, are identical or different, where at least one thereof is the halogen group or the alkyl halide group, where a7, f7, and n7 represent an integer number of 1 or
 2. b7 c7, and e7 represent one of integer numbers 1 to 4, where d7 represents 0 or one of integer numbers 1 to 4, and where g7 and m7 represent one of integer numbers 1 to
 3. 21. The battery according to claim 20, wherein: the compound shown in Chemical formula 17 includes at least one selected from the group consisting of difluoro[oxalate-O,O′]lithium borate in Chemical formula 20(1), difluorobis[oxalate-O,O′]lithium phosphate in Chemical formula 20(2), difluoro[3,3,3-trifluoro-2-oxide-2-trifluoromethyl propionate(2-)-O,O′]lithium borate in Chemical formula 20(3), bis[3,3,3-trifluoro-2-oxide-2-trifluoromethyl propionate(2-)-O,O′]lithium borate in Chemical formula 20(4), tetrafluoro[oxalate-O,O′]lithium phosphate in Chemical formula 20(5), and bis[oxalate-O,O′]lithium borate in Chemical formula 20(6); the compound shown in Chemical formula 18 includes at least one selected from the group consisting of (2,2-difluoromalonate oxalate)lithium borate in Chemical formula 21(1), [bis(3,3,3-trifluoromethyl)glycolate oxalate]lithium borate in Chemical formula 21(2), (3,3,3-trifluoromethyl propionate oxalate)lithium borate in Chemical formula 21(3), (2-trifluoromethyl propionate oxalate)lithium borate in Chemical formula 21(4), (4,4,4-trifluoro-3-trifluoromethyl butyric acid oxalate)lithium borate in Chemical formula 21(5), (perfluoropinacolate oxalate)lithium borate in Chemical formula 21(6), (4,4,4-trifluoro-3-methyl butyric acid oxalate)lithium borate in Chemical formula 21(7), and (4,4,4-trifluoro butyric acid oxalate)lithium borate in Chemical formula 21(8); and the compound shown in Chemical formula 19 includes fluorotrifluoromethyl[oxalate-O,O′]lithium borate in Chemical formula 21(9):


22. The battery according to claim 12, wherein the electrolyte salt contains at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, and compounds shown in Chemical formula 22, Chemical formula 23, and Chemical formula 24: LiN(C_(m)F_(2m+1)SO₂)(C_(n)F_(2n+1)SO₂)  Chemical formula 22 where m and n represent an integer number of 1 or more, and where m and n may be identical or different:

where R81 represents a straight chain or branched perfluoro alkylene group with the carbon number in the range from 2 to 4: LiC(C_(p)F_(2p+1)SO₂)(C_(q)F_(2q)1SO₂)(C_(r)F_(2r+1)SO₂)  Chemical formula 24 where p, q, and r represent an integer number of 1 or more, and where p, q, and r are identical or different.
 23. The battery according to claim 12, wherein the anode contains a material containing as an element a carbon material, lithium metal, or at least one selected from the group consisting of silicon (Si) and tin (Sn).
 24. The battery according to claim 12, wherein the anode contains at least one selected from the group consisting of a simple substance of silicon, an alloy of silicon, a compound of silicon, a simple substance of tin, an alloy of tin, and a compound of tin.
 25. The battery according to claim 12, wherein the anode comprises: an anode current collector; and an anode active material layer provided on the anode current collector, wherein the anode active material layer is formed by at least one method selected from the group consisting of vapor-phase deposition method, liquid phase deposition method, and firing method. 